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Abstract:

Disclosed is a gas barrier film which has both high gas barrier
performance and high cracking (bending) resistance. Specifically
disclosed is a gas barrier film which comprises, on a substrate in the
following order, at least one silanol-containing layer and at least one
gas barrier layer that contains silicon atoms and hydrogen atoms. The gas
barrier film is characterized in that the relative SiOH ion strength in
the central part of the silanol-containing layer in the film thickness
direction as detected by time-of-flight secondary ion mass spectrometry
(Tof-SIMS) is 0.02-1.0 when the relative Si ion strength is taken as 1.
Also disclosed is an organic photoelectric conversion element which
comprises the gas barrier film.

Claims:

1. A gas barrier film comprising a substrate having thereon at least one
silanol-containing layer and at least one gas barrier layer in that
order, the gas barrier layer containing silicon atoms and oxygen atoms,
wherein a relative SiOH ionic strength detected from a central portion of
the silanol-containing layer with respect to the depth direction thereof
is from 0.02 to 1.0, provided that a relative Si ionic strength is set to
1.0, the relative SiOH ionic strength and the relative Si ionic strength
being detected via time-of-flight secondary ion mass spectroscopy
(Tof-SIMS).

2. The gas barrier film of claim 1, wherein the relative SiOH ionic
strength is from 0.2 to 0.8.

3. The gas barrier film of claim 1, wherein the relative SiOH ionic
strength is from 0.3 to 0.6.

4. The gas barrier film of claim 1, wherein the gas barrier film
comprises a second gas barrier layer between the substrate and the
silanol-containing layer.

5. The gas barrier film of claim 1, wherein the substrate comprises a
plastic film.

6-10. (canceled)

11. The gas barrier film of claim 1, wherein a rate of water vapor
permeation is 10.sup.-4 g/(m224 h) or less, and a rate of oxygen
permeation is 0.01 ml/(m.sup.20.1 MPa/day) or less.

12. The gas barrier film of claim 1, wherein a rate of water vapor
permeation is 10.sup.-5 g/(m224) or less, and a rate of oxygen
permeation is 0.001 ml/(m.sup.20.1 MPa/day) or less.

13. A method of manufacturing a gas barrier film of claim 1, wherein at
least one of the silanol-containing layer and the gas barrier layer is
prepared through a step of applying a liquid containing a silicon
compound.

14. The method of claim 13, wherein the silanol-containing layer is
prepared through a step of applying a liquid containing a silicon
compound.

15. The method of claim 13, wherein the gas barrier layer is prepared
through a step of applying a liquid containing a silicon compound.

16. The method of claim 13, wherein the silanol-containing layer or the
gas barrier layer is prepared via an ultraviolet light irradiation
treatment carried out on a film obtained by applying the liquid
containing a silicon compound from a surface side of the film obtained by
applying the liquid containing the silicon compound.

17. A method of manufacturing a gas barrier film of claim 1, wherein the
silanol-containing layer or the gas barrier layer is prepared via an
ultraviolet light irradiation treatment carried out on a film obtained by
applying a liquid containing a silicon compound from a surface side of
the film obtained by applying the liquid containing the silicon compound.

Description:

FIELD OF THE INVENTION

[0001] The present invention relates to a gas barrier film mainly used for
packaging an electronic device, an organic photoelectric conversion
element (a solar cell), or display materials, for example, an organic
electroluminescent element (hereafter, also referred to as an organic EL
element) and a plastic substrate of a liquid crystal display, and also
relates to a manufacturing method thereof and an organic photoelectric
conversion element employing the gas barrier film.

BACKGROUND OF THE INVENTION

[0002] A barrier film in which a thin layer of a metal oxide such as
aluminum oxide, magnesium oxide, or silicon oxide is formed on the
surface of a plastic substrate or a film has been widely used for
packaging a product which requires blocking of various types of gases
such as water vapor and oxygen or for packaging to prevent a quality
change of, for example, food, industrial products or medical products.

[0003] Also, aside from the use for packaging, barrier films have been
used as a substrate for liquid crystal displays, photoelectric conversion
elements (also referred to as solar cells), or organic electroluminescent
device substrates (also referred to as organic EL device substrates).

[0004] Aluminum foil has been widely used as a packaging material in this
field, however, disposal after use is becoming a problem, and, in
addition, since aluminum foil is basically an opaque material, it has the
inherent problem that it is difficult to check the content from outside.
Further, it is difficult to be used as a material for a solar cell which
requires transparency.

[0005] Specifically, for a transparent substrate of which application to a
liquid crystal display, an organic EL element or a solar cell is in
progress, added has been a higher level of requirement, for example,
capability of roll-to-roll production of the substrate, durability for a
long duration, freedom of shape, and capability of curved display, in
addition to the requirements of weight saving and a large scale.
Replacement of a glass substrate, which is heavy, fragile and difficult
in increasing the size with a film substrate such as a transparent
plastic, is also in progress.

[0006] However, there has been a problem in that the gas barrier property
of a film substrate such as a transparent plastic film is inferior to
that of a glass substrate. For example, when such a substrate having an
insufficient gas barrier property is used as a substrate of an organic
photoelectric conversion element, water vapor or air may penetrate the
substrate, which may cause degradation of the photoelectric conversion
efficiency or durability due to deterioration of the organic film.

[0007] When a polymer substrate is used as a substrate of an electronic
device, problems may occur that oxygen permeates the polymer substrate
and soaks and spreads in an electron device to deteriorate the device,
and that the degree of vacuum required in an electron device cannot be
maintained.

[0008] In order to overcome such a problem, a technique to provide a thin
metal oxide layer on a film substrate to obtain a gas barrier film
substrate has been known. As a gas barrier film used for a packaging
material or for a liquid crystal display, a plastic film on which a
silicon oxide (for example, refer to Patent Document 1) or an aluminum
oxide (for example, refer to Patent Document 2) is vacuum evaporated has
been known.

[0009] As a method to form a film via a simple coating process, instead of
a vacuum evaporation method which needs a vacuum process, there have been
known several methods to form a gas barrier film composed of a converted
silica film obtained by conducting a conversion treatment on a film
formed by applying a coating liquid containing a silicon compound such as
polysilazane (for example, refer to Patent Documents 3, 4 and 5).

[0010] Specifically, in Patent Document 4, disclosed has been a process in
which a coated film of polysilazane is converted to a silica film via an
oxygen plasma discharge treatment carried out under atmospheric pressure,
in which formation of a gas barrier layer without using a vacuum system
can be carried out.

[0011] However, the rate of water vapor permeation of the obtained film is
0.35 g/(m224 h), which cannot be said to be capable of using in a
device such as described above. Generally, it is said that the rate of
water vapor permeation desired for a gas barrier layer applied for an
organic photoelectric conversion element is necessary to be much less
than 1×10-2 g/(m224 h).

[0012] Also, as a method to form a gas barrier layer via an atmospheric
pressure plasma discharge method, a film forming method in which high
energy density and stable plasma discharge is possible has been proposed
(for example, refer to Patent Documents 6 and 7).

[0013] In above mentioned Patent Documents 6 and 7, in order to prevent
cracking which occurs when a silica film having a high barrier property
is formed on a flexible plastic film, such as polyethylene terephthalate
(PET), a stress relaxation design has been adopted, in which the barrier
layer has a distribution of carbon content along the thickness direction
of the layer and the hardness of the film becomes lower when coming
closer to the substrate.

[0014] However, since it is a CVD film formation method, it has been
revealed that, particles are generated in the plasma space as a
byproduct, and that such particles adhere to the substrate, whereby
uniform film formation may suffer. It is highly possible that particles
generated in such a manner become a starting point of a barrier defect.
Accordingly, this method cannot be fully recommended to be a method to
stably form a uniform gas barrier layer.

[0015] When a gas barrier film having a certain extent of thickness is
formed on a plastic film, the silica film is extremely brittle, when a
high density silica film having a uniform density (or uniform hardness)
along the thickness direction of the film is formed, whereby cracking
frequently occurs. Accordingly, there has been a large limitation in the
handling method or in a using method, which has been a big drawback. For
example, a roll-to-roll process has not been able to be used as a method
of forming a gas barrier layer, shipment conveyance in the roll shape has
not been possible, and, when the gas barrier layer is used in an organic
photoelectric conversion element, the element cannot be used on a curved
surface. These have been the problems in the manufacturing of a gas
barrier film employing a roll-to-roll method under atmospheric pressure.

[0016] However, it has been desired in this technical field to realize
stable manufacturing of a uniform gas barrier film which is applicable
to, for example, a substrate of an organic photoelectric conversion
element, while satisfying both a high gas barrier property and cracking
(or bending) resistance, employing a roll-to-roll method under
atmospheric pressure.

[0024] An object of the present invention is to provide a gas barrier film
which satisfies both a high gas barrier property and cracking (or
bending) resistance, a stable manufacturing method of a uniform gas
barrier film employing a roll-to-roll method carried out under an
atmospheric pressure, and an organic photoelectric conversion element
employing the gas barrier film.

Means to Solve the Problems

[0025] The object of the present invention is achieved by the following
structure.

[0026] 1. A gas barrier film comprising a substrate having thereon at
least one silanol-containing layer and at least one gas barrier layer in
that order, the gas barrier layer containing silicon atoms and oxygen
atoms, wherein

[0027] a relative SiOH ionic strength detected from a central portion of
the silanol-containing layer with respect to the depth direction thereof
is from 0.02 to 1.0, provided that a relative Si ionic strength is set to
1.0, the relative SiOH ionic strength and the relative Si ionic strength
being detected via time-of-flight secondary ion mass spectroscopy
(Tof-SIMS).

[0028] 2. The gas barrier film of Item 1, wherein the relative SiOH ionic
strength is from 0.2 to 0.8.

[0029] 3. The gas barrier film of Item 1, wherein the relative SiOH ionic
strength is from 0.3 to 0.6.

[0030] 4. The gas barrier film of any one of Items 1 to 3, wherein the gas
barrier film comprises a second gas barrier layer between the substrate
and the silanol-containing layer.

[0031] 5. The gas barrier film of any one of Items 1 to 4, wherein the
substrate comprises a plastic film.

[0032] 6. A method of manufacturing a gas barrier film of any one of Items
1 to 5, wherein the silanol-containing layer is prepared through a step
of applying a liquid containing a silicon compound.

[0033] 7. A method of manufacturing a gas barrier film of any one of Items
1 to 5, wherein the gas barrier layer is prepared through a step of
applying a liquid containing a silicon compound.

[0034] 8. A method of manufacturing a gas barrier film of any one of Items
1 to 5, wherein the silanol-containing layer or the gas barrier layer is
prepared through a step of applying a liquid containing a silicon
compound.

[0035] 9. A method of manufacturing a gas barrier film of any one of Items
1 to 5, wherein the silanol-containing layer or the gas barrier layer is
prepared via an ultraviolet light irradiation treatment carried out on a
film obtained by applying a liquid containing a silicon compound from a
surface side of the film obtained by applying the liquid containing the
silicon compound.

[0036] 10. An organic photoelectric conversion element comprising the gas
barrier film of any one of Items 1 to 5.

Effect of the Invention

[0037] According to the present invention, a gas barrier film which
satisfies both a high gas barrier property and a cracking (or bending)
resistance property, a stable manufacturing method of a uniform gas
barrier film employing a roll-to-roll method carried out under an
atmospheric pressure, and an organic photoelectric conversion element
employing the gas barrier film could be provided.

[0039] FIG. 2 is a cross-sectional figure illustrating a solar cell
composed of an organic photoelectric conversion element equipped with a
photoelectric conversion layer having a p-i-n three layer structure.

[0051] In the present invention, a gas barrier film which satisfies both a
high gas barrier property and a cracking (or bending) resistance property
can be provided according to the constitution described in any one of
claims 1-5, a stable manufacturing method of a uniform gas barrier film
employing a roll-to-roll method carried out under an atmospheric pressure
can be provided according to the constitution described in any one of
claims 6-8, and an organic photoelectric conversion element employing the
gas barrier film can also be provided.

[0052] The present invention, the constituting elements thereof and
embodiments to carry out the present invention will be explained below.

<<Gas Barrier Film (Also Referred to as Gas Barrier Nature
Film)>>

[0053] The gas barrier film of the present invention will be explained.

[0054] In the present invention, a gas barrier film which satisfies both a
high gas barrier property and cracking (or bending) resistance is
provided by having a structure in which the gas barrier film has a
substrate having thereon at least one silanol-containing layer and at
least one gas barrier layer in that order, in which the gas barrier layer
contains silicon atoms and oxygen atoms, wherein a relative SiOH ionic
strength detected from a central portion of the silanol-containing layer
with respect to the depth direction thereof is from 0.02 to 1.0, provided
that a relative Si ionic strength is set to 1.0, the relative SiOH ionic
strength and the relative Si ionic strength being detected via
time-of-flight secondary ion mass spectroscopy (Tof-SIMS).

[0055] With respect to the gas barrier nature of the gas barrier film of
the present invention, the rate of water vapor permeation measured in
accordance with the method of JIS K 7129B (also referred to as degree of
water vapor permeation: at 25±0.5° C., under relative humidity:
90±2% RH) is preferably 10-3 g/(m224 h) or less, more
preferably 104 g/(m224 h) or less, and specifically preferably
10-5 g/(m224 h) or less.

[0056] The rate of oxygen permeation (also referred to as degree of oxygen
permeation) measured in accordance with the method of JIS K 7126-1987 is
preferably 0.01 ml/(m20.1 MPa/day) or less and more preferably 0.001
ml/(m20.1 MPa/day) or less.

[0057] Subsequently, each element which constitutes the gas barrier film
of the present invention will be explained.

[0058] At first, the silanol-containing layer in the present invention
will be explained.

<<Silanol-Containing Layer>>

[0059] The silanol-containing layer according to the present invention
will be explained.

[0060] The silanol-containing layer according to the present invention
preferably has a relative SiOH ionic strength detected by a
time-of-flight secondary ion mass spectrometry (Tof-SIMS) in the film
depth direction of 0.02-1, provided that the relative Si ionic strength
is set to 1, more preferably, the relative SiOH ionic strength is
0.2-0.8, and further more preferably, the relative SiOH ionic strength is
0.3-0.6.

[0061] With respect to the silanol-containing layer according to the
present invention, it is a necessary condition that the above mentioned
relative SiOH ionic strength is at least 0.02 or more, and a layer of
which SiOH ionic strength is less than 0.02 is not defined as a
silanol-containing layer.

[0062] The relative SiOH ionic strength of 0.02-1.0 in a
silanol-containing layer can be achieved by applying the adjustment
method of the content of silanol group in the silanol-containing layer,
which will be mentioned later.

(Inclination of Content of Silanol Group in a Silanol Layer)

[0063] The inclination of the content of silanol groups in a silanol layer
means the state where the content of silanol groups which exist in a
silanol-containing layer is changing in the film depth direction with
regularity (it increases or decreases).

[0064] Here, the change of the content of silanol groups may be continuous
or may be stepwise. Also, the silanol-containing layer may have a
constant content ratio inclination throughout the thickness, or may have
a portion having a constant content ratio and a portion having a constant
content ratio inclination, in combination.

[0065] The content ratio inclination can be adjusted by suitably selecting
a treatment method in the film forming process.

[0066] The thickness range in which the content ratio has inclination is
preferably 20% or more of the thickness of a silanol-containing layer
which can be formed with a single application of a coating liquid. The
thickness range is more preferably 30% or more. It is specifically
preferable that a content ratio inclination is formed in the thickness
range of 40% or more.

(Adjustment Method of Content of Silanol Groups in Silanol Layer)

[0067] In the present invention, the content of silanol groups contained
in a silanol-containing layer can be adjusted by appropriately selecting
the material which forms a coated film, and a post-treatment or a
conversion treatment (also referred to as an oxidation treatment) of the
coated film.

[0068] For example, by keeping a polysilazane coated film under a high
humidity condition for a certain period of time, the silanol conversion
reaction can be intentionally promoted to prepare a silanol-containing
layer having a uniform and high silanol content, or a layer constitution
having a silanol content inclination along the thickness direction can be
obtained by irradiating the polysilazane coated film with light from the
film surface side or by conducting an atmospheric pressure plasma
treatment.

[0069] Alternatively, since the reactivity of a silica conversion reaction
can be controlled by appropriately adjusting the species and the amount
of catalyst contained in polysilazane, it becomes possible to adjust the
content ratio of silanol groups to a desired value, in combination with
the above mentioned treatment.

[0071] Time-of-flight secondary ion mass spectrometry is generally called
Tof-SIMS (Tof-SIMS: Time-Of-Flight Secondary Ion Spectrometry). As the
principle, a sample is irradiated with a pulse-like ion under high
vacuum, and the ion torn off from the sample surface due to a sputtering
phenomenon is detected after classifying based on weight (atomic weight
or molecular weight). The chemical species (an atom or a molecule)
existing on the outermost surface of the sample can be deduced from the
weight and the pattern of the amount of detection (namely, a mass
spectrum).

[0072] In more detail, the analysis is carried out via the following two
steps.

[0073] (1) Emission of secondary ion: The solid state sample surface is
irradiated with ions (primary ions) in pulses, and varieties of particles
are emitted from the sample surface being subjected to ion bombardment
due to a sputtering phenomenon.

[0074] Specifically, in Tof-SIMS, the current density of primary ions is
suppressed at a low level (a static mode) to carry out sputtering so that
damage of the sample surface is suppressed as low as possible.

[0075] (2) Mass separation and detection: The ions (secondary ions)
existing in the particles emitted via sputtering are picked up and
detected after classifying based on the weight (the mass), whereby a
composition analysis from the surface to the interior of a sample is
conducted, which is called as a secondary ion mass spectrum analysis.

[0076] In Tof-SIMS, a time-of-flight type analysis equipment is adopted
for mass separation. After the ions are caught in a flight tube via an
electric field, the ions fly in the flight tube, and lighter ions arrive
faster at a detector and heavier ions arrive later at a detector.

[0077] This time of flight is converted into mass to conduct mass
separation. The use of a time-of-flight type analysis equipment enables a
high sensitivity, high mass resolution, and high mass value detection.

[0078] By using this method, not only a two dimensional distribution of
chemical species existing on the surface can be determined, but also a
compositional analysis of elements along the depth direction of the
sample of a shallow region can be conducted by repeatedly digging the
surface with an ion beam. Further, determination of relative existing
amounts of detected ions can be carried out.

(Method to Determine Relative SiOH Ionic Strength)

[0079] Subsequently, a method to determine a relative SiOH ion strength
according to the present invention will be explained.

[0080] As described above, the SiOH ionic strength of the present
invention can be obtained by using time-of-flight secondary ion mass
spectrometry.

[0081] The SiOH ionic intensity or SiOH ionic intensity of the present
invention is obtained as an average value of each detected ionic strength
obtained by measuring in the depth direction of a silanol-containing
layer at two-dimensionally randomly selected two points.

[0082] Further, the relative SiOH ionic strength according to the present
invention is obtained as a value of relative SiOH ionic strength when
relative Si ionic strength is normalized to 1.

[0083] As mentioned above, in Tof-SIMS, the analysis along the depth
direction from the surface is possible by using sputtering by ion (Ar,
Xe) irradiation in combination.

[0084] Measurement along the film depth direction of a silanol-containing
layer is performed by repeating sputtering and measurement at a certain
interval until the substrate adjoining the silanol-containing layer or
another layer adjoining the silanol-containing layer on the substrate
side is exposed while using the outermost surface free from contamination
or foreign substance as a starting point.

[0085] As a measuring interval, 30 seconds-3 minutes as a sputtering time
is adopted, however, the measuring interval is preferably 30 seconds-1
minute, since the measuring interval is preferably as short as possible.

[0086] Since it is difficult to obtain a reliable result from the
outermost surface due to the effect of adsorbed water or other adsorbed
substance, the value obtained after 2 minutes from start sputtering is
used as a value from the outermost surface, and as a terminal point of
the silanol-containing layer (namely, the interface between the substrate
or between an adjoining layer on the substrate side), adopted is the
point which is one point before the point at which a component originated
from the substrate adjoining the silanol-containing layer or another
layer adjoining the silanol-containing layer on the substrate side (for
example, c ions when a plastic substrate is used) begins to be
drastically detected (by several orders of magnitude).

[0087] The measured values at the above mentioned outermost surface and
the terminal point on the substrate side of the silanol-containing layer
are designated as the values detected along the depth direction of the
silanol-containing layer, and the ionic strengths at these points are
used as the ionic strength according to the present invention.

[0088] In the present invention, a relative SiOH ionic strength detected
via time-of-flight secondary ion mass spectrometry (Tof-SIMS) at the
central portion of the layer in the depth direction of a
silanol-containing layer is determined. Here, "at the central portion of
the layer" specifically means that the measurement is conducted at a
depth of 100 nm±10 nm (namely, ±5% based on the layer thickness)
from the surface of the silanol-containing layer when the layer thickness
of the silanol-containing layer is 200 nm.

[0089] When a film component has distribution in the depth direction of
the film and a composition of the film is not uniform, the sputtering
rate (namely, thickness per unit time at which sputtering is carried out)
may not be exactly constant, however, in the present invention, the above
mentioned method would not cause a problem since it is not necessary to
exactly specify the central portion of the layer in the present
invention.

[0090] By providing a silanol-containing layer according to the present
invention between a substrate and a gas barrier layer, the resistance for
bending the gas barrier film of the present invention can be
significantly improved.

[0091] Namely, the following excellent effects can be obtained, for
example, a high gas barrier property can be maintained even when a gas
barrier film is manufactured via a roll-to-roll method and shipped and
conveyed in a roll form, and, when a gas barrier film is used for a
device such as an organic photoelectric conversion element, the device
can be equipped on a curved surface.

[0092] The content of silanol groups contained in a silanol-containing
layer may be made constant throughout the layer or may be made to have
inclination along the depth direction of the layer.

[0093] Specifically, a resistance for bending the film is expected to be
improved by providing a higher content of silanol groups in the region
closer to the substrate and providing a lower content of silanol groups
in the region closer to the gas barrier film due to enhanced
stress-relaxation function.

[0094] Next, the gas barrier layer according to the present invention will
be explained.

<<Gas Barrier Layer (Layer which has Gas Barrier Property)>>

[0095] The gas barrier layer according to the present invention is a layer
(also called as a film) which contains silicon atoms and oxygen atoms as
constituting atoms, and prevents the permeation of oxygen or water vapor.

[0096] As a material which constitutes a gas barrier layer, an inorganic
oxide which has silicon is specifically preferred, and a layer which has,
for example, silicon oxide or silicon nitride oxide may be cited.

[0097] At first, the method of manufacturing the gas barrier layer
according to the present invention will be explained.

(Method of Manufacturing Gas Barrier Layer)

[0098] As the method of manufacturing a gas barrier layer according to the
present invention, it is preferred that, after applying a solution
containing a silicon compound onto a surface to be provided with a film,
the applied layer is subjected to a light irradiation treatment or a
plasma treatment under an oxidizing gas atmosphere.

[0099] The light irradiation treatment or the plasma treatment carried out
under an oxidizing gas atmosphere is more preferably conducted in
combination with a heat treatment.

[0100] With respect to the plasma treatment carried out under an oxidizing
gas atmosphere, methods known in the art such as a vacuum oxygen plasma
method are applicable, however, it is preferable that an atmospheric
pressure plasma method be used.

[0101] The layer formation via application of a solution containing a
silicon compound, formation of a gas barrier layer via an oxidation
treatment (also referred to as a conversion treatment) of the layer, and,
subsequently, the feature of the obtained gas barrier layer will be
explained, in turn, below.

[0102] The preparation of a solution containing a silicon compound and the
formation of a coated film via application of the solution according to
the present invention will be explained.

[0103] In the preparation of a solution containing a silicon compound
according to the present invention, a solvent which tends not to contain
water, for example, xylene, dibutylether, solvesso or turpentine is
preferably employed in order to avoid the reaction of water with the
solution while being applied.

[0104] As a method to apply the solution containing a silicon compound, an
arbitrary and suitable method may be employed, examples of which include
a spin coat method, a roll coat method, a flow coat method, an inkjet
method, a spray coat method, a printing method, a dip coating method, a
casting film formation method, a bar coat method and a gravure printing
method.

[0105] The coated film (applied film) formed by applying the solution
containing a silicon compound is subjected to a conversion treatment
(also referred to as an oxidizing treatment) which will be described
later, whereby the silicon compound is converted to a silicon dioxide to
form a gas barrier layer.

[0107] In a preferable embodiment, the coated film is annealed in order to
obtain a uniform dried film after the solvent is removed. The annealing
temperature is preferably 60° C.-200° C. and more
preferably 70° C.-160° C. The duration of annealing is
preferably 5 seconds--around 24 hours and more preferably 10
seconds--around 2 hours.

[0108] A uniform coated layer can be stably obtained by conduct annealing
in the above described range before conducting a conversion treatment
which is followed by the subsequent step.

[0109] Further, annealing may be conducted at a constant temperature, the
temperature may be changed stepwise, or the temperature may be changed
continuously (increasing temperature and/or decreasing temperature).
While annealing, in order to stabilize the reaction, humidity is
preferably adjusted, and the humidity is normally from 30% RH to 90% RH,
and more preferably from 40% RH to 80% RH.

[0110] Subsequently, silicon compounds will be explained.

(Silicon Compound)

[0111] The silicon compounds according to the present invention will be
explained.

[0112] The silicon compound according to the present invention is not
specifically limited as far as it enables preparation of a coating liquid
containing a silicon compound, however, a polysilazane compound or a
polysiloxane is preferably used.

[0113] Here, silicon dioxide (namely, SiO2 (also referred to as
silica)) is not included an the silicon compound according to the present
invention.

[0117] The gas barrier layer according to the present invention is formed
by canying out conversion treatment (or an oxidation treatment) on the
coated film containing the above mentioned silicon compound. As a
conversion treatment, methods to conduct a light irradiation treatment or
a plasma treatment under an oxidizing atmosphere are preferably used.

[0118] In the following sections, an atmospheric pressure plasma treatment
which is one of the preferable embodiments among the plasma treatments
applied for the conversion treatment (or an oxidizing treatment) will be
explained, and, subsequently, a light irradiation treatment will be
explained.

(Atmospheric Pressure Plasma Treatment)

[0119] The atmospheric pressure plasma treatment which is preferably used
for forming a gas barrier layer according to the present invention will
be explained.

[0120] In the case of the atmospheric pressure plasma treatment, nitrogen
gas and/or an element of the 18th group in the periodic table, in more
concretely, helium, neon, argon, krypton, xenon or radon is preferably
used as a discharge gas. An oxidation reaction can be promoted by
supplying oxygen having an oxidizing nature as a reaction gas. Of these,
nitrogen, helium and argon are preferably used, and, specifically,
nitrogen is most preferably used also in view of the low cost.

[0121] A reaction gas used for the atmospheric pressure plasma treatment
can be selected according to a purpose, and a hydrogen gas, a nitrogen
gas, an oxygen gas or water vapor is preferably used, and a hydrogen as
or an oxygen gas is more preferably used.

[0122] With respect to the atmospheric pressure plasma treatment in the
present invention, concretely, it is preferable that two or more electric
fields having different frequencies are applied in the discharge space by
applying an electric field obtained by superposing a first high frequency
electric field and a second high frequency electric field as disclosed in
WO 2007/026545 pamphlet.

[0123] The frequency of the aforementioned second high frequency electric
field ω2 is higher than the frequency of the aforementioned first
high frequency electric field ω1, the relationship among the
strength of the first high frequency electric field V1, the strength of
the second high frequency electric field V2 and the strength of the
discharge initiating electric field IV meets

V1≧IV>V2 or V1>IV V2,

and the power density of the second high frequency electric field is 1
W/cm2 or more.

[0124] By employing such an electric discharge condition, for example,
even nitrogen gas having a high discharge initiating electric field can
initiate discharge, a high density and stable plasma state can be
maintained, and highly efficient thin film formation can be carried out.

[0125] When nitrogen is used as a discharge gas by the above-mentioned
measurement, the strength of a discharge initiating electric field IV
(1/2Vp-p) is around 3.7 kV/mm. Nitrogen gas is excited to cause a plasma
state by applying an electric field of which the strength of the first
high frequency electric field meets V1≧3.7 kV/mm in the
above-mentioned relationship.

[0126] Here, as the frequency of the first power source, 200 kHz or less
is preferably used. Further, the wave shape of the electric field may be
a continuous wave or a pulse wave. The lower limit is preferably 1 kHz or
less.

[0127] On the other hand, as the frequency of the second power source, 800
kHz or more is preferably used. The higher the frequency of the second
power source is, the higher the density of the plasma is, whereby a dense
and high quality thin film can be obtained. The higher limit is
preferably around 200 MHz.

[0128] Regarding application of high frequency electric fields from such
two electric sources, the first high frequency electric field is
necessary to start the electric discharge of a discharge gas which
require a high strength of discharge initiating electric field, and a
dense and high quality thin film can be obtained due to a high plasma
density caused by the high frequency and the high power density of the
second high frequency electric field.

[0129] Next, preferable embodiments of the light irradiation treatment
will be explained.

<<Light Irradiation Treatment>>

[0130] In the light irradiation treatment according to the present
invention, the light used for the light irradiation treatment under an
oxidizing treatment gas atmosphere is preferably ultraviolet light. Via
irradiation of ultraviolet light, active oxygen and ozone are generated.
These active oxygen and ozone further promote the oxidizing reaction.

[0131] The reactivity of these active oxygen and ozone is extremely high,
for example, when polysilazane is chosen as a silicon compound, a coated
film of polysilazane which is a precursor of a silicon oxide is directly
oxidized without going through silanol, whereby a higher density silicon
oxide film containing fewer defects can be formed.

[0132] As a method to compensate the insufficiency of reactive ozone with
a method other than irradiation of light, ozone may be generated by a
method known in the art, for example, via discharge, to introduce the
ozone into an ultraviolet light irradiating portion.

[0133] The wavelength of ultraviolet light used for this purpose is not
specifically limited, however, it is preferably 100 nm-450 nm. It is more
preferable that vacuum ultraviolet light having a wavelength of 150 nm to
about 300 nm is used.

[0134] As a light source, for example, a low pressure mercury lamp, a
deuterium lamp, a xenon excimer lamp, a metal halide lamp and an excimer
laser are usable. The output power of a lamp is preferably from 400 W to
30 kW. The illumination intensity is preferably from 100 mW/cm2 to
100 kW/cm2. The illumination energy is preferably from 10
mJ/cm2 to 5000 mJ/cm2, and more preferably from 100 mJ/cm2
to 2000 mJ/cm2. The illumination intensity of ultraviolet light
illumination is preferably from 1 mW/cm2 to 10 W/cm2.

[0135] Of these, vacuum ultraviolet light of which wavelength is from 100
nm to 200 nm is most preferably used, whereby an oxidizing reaction can
be carried out at a lower temperature in a shorter time. As a light
source, a rare gas excimer lamp, such as a xenon excimer lamp, is most
preferably used.

[0136] By irradiating a coated film of polysilazane with ultraviolet light
under an oxidizing gas atmosphere, the polysilazane is converted to a
high density silicon oxide film, namely, a high density silica film. The
film thickness and the density of the silica film can be controlled by
the intensity, irradiation time and wavelength of the ultraviolet light,
which are appropriately selected by selecting the kind of a lamp to
obtain a desired film structure. Also, plural times of irradiation may be
conducted instead of continuous irradiation, in which the plural times of
irradiation may be of short time irradiation or pulse irradiation.

[0137] Heating the coated film simultaneously with ultraviolet light
irradiation is also preferably conducted to promote the reaction (namely,
an oxidizing reaction or a conversion treatment). As a method of heating,
for example, a method to heat the coated film by contacting the substrate
with a heating element such as a heat block to heat the coated film via
thermal conduction; or a method to use light of an infrared region such
as an IR heater; may be cited, however, the method is not specifically
limited. A method in which flatness of the coated film can be maintained
may be arbitrarily selected.

[0138] The heating temperature is preferably in the range of 500°
C. to 200° C., and more preferably in the range of 80° C.
to 150° C. The heating duration is preferably in the range of 1
second to 10 hours, and more preferably in the range of 10 seconds to 1
hour.

(Feature of Gas Barrier Film)

[0139] The feature of the gas barrier film according to the present
invention will be explained.

[0140] The thickness of the gas barrier layer is preferably in the range
of 30 nm to 2000 nm, more preferably in the range of 40 nm to 500 nm, and
specifically preferably in the range of 40 nm to 300 nm, in order to
effectively avoid deterioration of the barrier property or generation of
cracks due to a foreign substance or protrusion on the film forming
surface.

[0141] The gas barrier layer according to the present invention may be
constituted of a single layer or a plurality of similar layers, and by
providing a plurality of layers, the gas barrier property can be
improved.

[0142] With respect to a gas barrier layer and a silanol-containing layer,
the gas barrier layer and the silanol layer may be simultaneously formed
with one film formation by, for example, conducting a treatment in which
a solution containing a silicon compound is applied to form one layer,
followed by conducting a conversion treatment (or an oxidizing treatment)
to a gas barrier layer only of the surface of the located layer while
adjusting so that silanol groups are left in interior of the film.

[0143] Further, it is also possible to have a constitution in which gas
barrier layers and silanol-containing layers are alternatively laminated.

[0144] Of these, with respect to the gas barrier film of the present
invention, it is preferable to have a constitution in which a second gas
barrier layer is provided between the substrate and the
silanol-containing layer.

[0145] Here, a second gas barrier layer will be explained.

<<Second Gas Barrier Layer>>

[0146] The second gas barrier layer according to the present invention
will be explained.

[0147] The second gas barrier layer according to the present invention is
at least one layer which is provided between a substrate and a
silanol-containing layer.

[0148] The second gas barrier layer according to the present invention may
be formed with a similar material, constitution and forming method to
those mentioned above.

[0149] By providing a second gas barrier layer, for example, an effect to
prevent deterioration due to aging under a high temperature condition can
be obtained, since the silanol-containing layer is sandwiched between two
films each having a high gas barrier property (namely, a gas barrier
property against water vapor or oxygen), whereby the durability of the
gas barrier layer is improved.

[0150] With respect to the deterioration due to aging under a high
temperature condition, it is afraid that deterioration due to aging under
a high temperature condition may occur, since, for example, silanol
groups in the silanol-containing layer tends to cause a
dehydration-condensation reaction.

[0151] On the other hand, decrease in the content of silanol groups may be
relatively suppressed when polysilazane of non-catalyst type is used as a
silicon compound, since heat energy of 450° C. or more is
necessary for silanol groups to conduct a dehydration-condensation,
accordingly, this reaction hardly occurs. However, the deterioration due
to aging under a high temperature condition can be further suppressed by
providing a second gas barrier layer.

[0152] Further, the surface energy of a substrate surface may become a
problem with respect to a coating property. Accordingly, an adhering
property of the substrate surface with a film formed thereon and a
coating property are important factors, since a poor coating property may
largely affect the gas barrier property. A surface obtained by providing
a second gas barrier layer is preferred, for example, because an effect
to improve the adhering property or a coating property can be expected.

<<Substrate>>

[0153] The substrate according to the gas barrier film of the present
invention will be explained.

[0154] The substrate according to the gas barrier film of the present
invention is not specifically limited as far as it is formed by a
material which can support the aforementioned silanol-containing layer or
the second gas barrier layer. The substrate according to the present
invention is preferably an organic substrate, namely, a plastic film,
having a smooth layer.

[0156] With respect to the cost or the ease of acquisition, for example,
polyethylene terephthalate (PET), polybutylene terephthalate and
polyethylenenaphthalate (PEN), polycarbonate (PC) are preferably used.
Alternatively, with respect to optical transparency, heat resistance and
adherence with an inorganic layer or a gas barrier layer, a heat
resistant transparent film containing silsesquioxane having an
organic-inorganic hybrid structure as a basic skeleton may be preferably
used.

[0157] The thickness of the substrate according to the present invention
is preferably 5 μm-500 μm and more preferably 25 μm-250 μm.

[0158] Further, the substrate according the present invention is
preferably transparent. It is because, when the substrate is transparent
and the layer formed on the substrate is also transparent, a transparent
barrier film can be obtained, whereby it is possible to use the barrier
film as a transparent substrate of, for example, a photoelectric
conversion element (or a solar cell).

[0159] A substrate being transparent means that the transmittance of
visible light (wavelengths of 400 nm-700 nm) is 80% or more.

[0160] The plastic film employing, for example, an above mentioned plastic
film may be a stretched film or a non-stretched film.

[0161] The plastic film substrate used in the present invention can be
produced by a common method well-known in the art. For example, by
melting a plastic used as a material in an extruding apparatus, and by
extruding the melt through a tubular die or a T-die to quench the melt, a
substantially amorphous, non-oriented and non-stretched substrate can be
obtained.

[0162] Also, a stretched substrate may be produced by stretching a
non-stretched substrate in a film conveyance direction (a longitudinal
direction) or a direction perpendicular to the film conveyance direction
(a transverse direction) via uniaxial stretching, sequential biaxial
stretching via a tenter method, simultaneous biaxial stretching via a
tenter method or simultaneous biaxial stretching via a tubular method.
The stretching ratio in this case is preferably 2-10 times in each of the
longitudinal axis direction and the transverse axis direction, although
the stretching ratio may be appropriately selected in accordance with the
resin as a raw material of the substrate.

[0163] Further, for a plastic film according to the present invention,
before providing a film, a surface cleaning treatment and a hydrophobic
treatment via a corona treatment or a UV ozone treatment are preferably
conducted to improve the adhesiveness and the coating property of the
formed film against the substrate surface.

[0164] Furthermore, an anchor coat agent layer may be provided on the
substrate surface according to the present invention for the purpose of
improving adhesiveness with a silanol-containing layer or a second gas
barrier layer.

[0165] Examples of an anchor coat agent used for the anchor coat agent
layer include a polyester resin, an isocyanate resin, an urethane resin,
an acrylic resin, an ethylene vinyl alcohol resin, a modified vinyl
resin, an epoxy resin, a modified styrene resin, a modified silicon
resin, and alkyltitanate, which may be used alone or in combination of
two or more kinds thereof.

[0166] A conventionally well-known additive agent can also be added to
these anchor coat agents. The anchor coating may be conducted by applying
an anchor coating agent such as described above on a plastic film via a
method known in the art, for example, a roll coat method, a photogravure
coat method, a knife coat method, a dip coat method, and a spray coat,
followed by drying to remove such as a solvent or a dilution agent.

[0167] The applying amount of the anchor coating agent as aforementioned
is preferably around 0.1 to 5 g/m2 (under a dried condition).

[0168] The substrate used in the present invention may be a film having a
gas barrier nature (for example, an aluminum foil, or an extremely thin
flexible glass sheet). By using such a substrate, it is possible for the
substrate to cover the function of a second gas barrier layer by itself.

(Smooth Layer)

[0169] The smooth layer of the present invention is provided in order to
flatten the crude surface of a transparent resin film having protrusions
or to flatten the transparent inorganic layer having asperity or pinholes
due to the protrusions existing on the transparent resin film substrate.
Such a smooth layer is basically formed by hardening a photosensitive
resin.

[0170] As a photosensitive resin used for a smooth layer, cited may be,
for example, a resin composition containing an acrylate compound having a
radically reactive unsaturated compound, a resin composition containing a
mercapto compound having an acrylate compound and a thiol group, and a
resin composition in which dissolved is a multifunctional acrylate
monomer such as an epoxy acrylate, an urethane acrylate, a polyester
acrylate, a polyether acrylate, a polyethyleneglycol acrylate, or
glycerol methacrylate. Further, it is also possible to use an arbitrary
mixture of the above resin composites. The photosensitive resin is not
specifically limited as far as it contains a reactive monomer having one
or more photopolymerizable unsaturated bond in the molecule.

[0172] The method of forming a smooth layer is not specifically limited,
however, preferably employed are wet methods, for example, a spin coating
method, a spray coating method, a blade coating method, and a dip coating
method, and dry coating methods, for example, a vacuum evaporation
method.

[0173] In the smooth layer forming process, an additive such as an
antioxidant, an ultraviolet absorber or a plasticizer may be added in the
aforementioned photosensitive resin, if needed. An appropriate resin or
an additive may be added in any smooth layer irrespective of the laminate
position in order to improve the film forming property or to avoid
occurrence of pin holes.

[0174] The flatness of a smooth layer is a value expressed by the surface
roughness, and the maximum profile peak height Rt (p) is preferably 10 nm
or more, but 30 nm or less. When the Rt(p) value is smaller than this
range, the coating property may be lost in the step of applying a silicon
compound, which will be described later, in the occasion when a coating
means becomes in contact with the smooth layer in a coating method such
as a wire bar method or a wireless bar method. Or, when the Rt(p) value
is smaller than this range, it may become difficult to smooth the
irregularity after applying a silicon compound.

[0175] The surface roughness is calculated from a cross-sectional curve of
the irregularity obtained by a continuous measurement using a detector
having a stylus of the minimal tip radius in an atomic force microscope
(AFM), which is a roughness relating the amplitude of minute irregularity
obtained by multiple measurements within a range of several tens μm
using a stylus of the minimal tip radius.

(Additive to Smooth Layer)

[0176] One of the preferable embodiments is that the aforementioned
photosensitive resin contains reactive silica particles on the surfaces
of which photosensitive groups having a photopolymerizable reactivity are
introduced (hereafter, also referred to merely as reactive silica
particles).

[0177] As a photosensitive group which has a photopolymerization property,
for example, cited is a polymerizable unsaturated group which is
represented by (meth)acryloyloxy group. The photosensitive resin may
contain a compound which enables a photopolymerization reaction with a
photosensitive group having a photopolymerizing reactivity, which is
introduced on the surfaces of reactive silica particles, for example, an
unsaturated organic compound having a polymerizable unsaturated group.

[0178] Further, as a photosensitive resin, a composition of which solid
content is adjusted by appropriately mixing a commonly used diluting
solvent with such reactive silica particles or an unsaturated organic
compound having a polymerizable unsaturated group.

[0179] The average diameter of the reactive silica particles is preferably
from 0.001 μm to 0.1 μm. By adjusting the average particle diameter
within such a range, a smooth layer having the following property becomes
easier to obtain, namely, a smooth layer having both an optical property
in which an anti-glare property and resolution are satisfied in a good
balance, which is an effect of the present invention, and a hard-coat
property.

[0180] In view of obtaining such an effect more easily, it is more
preferable to use reactive silica particles having an average particle
diameter of 0.001 μm to 0.01 μm.

[0181] The aforementioned inorganic particles are preferably contained in
the smooth layer in the mass ratio of the range of 20% to 60%, in view of
improving the adhesiveness of the smooth layer with the gas barrier
layer, preventing occurrence of cracks when the substrate is bent or
subjected to a heat treatment, and keeping an excellent optical property
regarding transparency and a refractive index of the gas barrier film.

[0182] In the present invention, used as silica particles may be a
substance in which silica particles are chemically bonded by forming a
silyloxy group between the silica particles via a hydrolytic
decomposition reaction of a hydrolysable silyl group of a hydrolyzable
silane modified with a polymerizable unsaturated group.

[0183] Examples of a hydrolytic silyl group include: carboxylate silyl
groups such as an alkoxy silyl group and an acetoxy silyl group;
halogenated silyl groups such as a chloro silyl group; an amino silyl
group; an oxime silyl group; and a hydrido silyl group.

[0184] Examples of a polymerizable unsaturated group include an
acryloyloxy group, a methacryloyloxy group, a vinyl group, a propenyl
group, a butadienyl group, a styryl group, an ethynyl group, a cinnamoyl
group, a malate group and an acrylamide group.

[0185] The thickness of the smooth layer used in the present invention is
preferably in the range of 1 μm to 10 μm and more preferably in the
range of 2 μm to 7 μm, in view of improving the smoothness of a
substrate, making it easy to adjust the balance in the optical property
of a substrate, and preventing the curl of a smooth film when a smooth
layer is provided only on one surface of a substrate.

[0186] Further, a bleed out prevention layer may be provided on the
substrate according to the present invention.

(Bleedout Preventing Layer)

[0187] A bleedout preventing layer is preferably provided on the surface
of a substrate opposite to the surface on which the smooth layer is
provided, in order to avoid the contamination of the contact layer due to
the migration of such as an unreacted oligomer from the inside of the
substrate to the surface, when a film having a smooth layer is heated. As
far as the bleedout preventing layer has this function, the bleedout
preventing layer may have the same constitution as that of the smooth
layer.

[0188] As an unsaturated organic compound having a polymerizable
unsaturated group, which may be incorporated in a bleedout prevention
layer, a polyvalent unsaturated organic compound having two or more
polymerizable unsaturated groups in the molecule or a monovalent
unsaturated organic compound having one polymerizable unsaturated group
in the molecule may be cited.

[0189] As other additive agents, a matting agent may be incorporated. As a
matting agent, inorganic particles having an average particle diameter of
0.1-5 μm are preferably used.

[0190] As such inorganic particles, one kind or two or more kinds in
combination of silica, alumina, talc, clay, calcium carbonate, magnesium
carbonate, barium sulfate, aluminum hydroxide, titanium dioxide or
zirconium dioxide may be used.

[0191] The matting agent containing inorganic particles is desirably
contained in a ratio of 2 mass parts or more, preferably 4 mass parts or
more, and more preferably 6 mass parts or more, but 20 mass parts or
less, preferably 18 mass parts or less, and more preferably 16 mass parts
or less, in the solid content of the bleedout preventing layer of 100
mass parts.

[0192] In the bleedout preventing layer, for example, a thermoplastic
resin, a thermo-curable resin, an ionization radiation-curable resin, or
a photopolymerization initiator, as a component other than a hard-coat
agent and a matting agent, may further be incorporated.

[0193] The aforementioned bleedout preventing layer can be prepared by:
preparing a coating liquid obtained by mixing a hard coat agent, a
matting agent, and other component, if necessary, and by appropriately
using a diluting solvent, if necessary; and applying the coating liquid
on the surface of a substrate film according to a method known in the
art, followed by irradiating the substrate with ionization radiation.

[0194] Examples of a method to irradiate the substrate with ionization
radiation include: irradiating the substrate with ultraviolet light
having a wavelength range of 100-400 nm, preferably 200-400 nm from a
very-high-pressure mercury lamp, a high-pressure mercury lamp, a
low-pressure mercury lamp, a carbon are or a metal halide lamp; and
irradiating the substrate with an electron beam having a wavelength of
100 nm or less from a scanning type or a curtain type electron beam
accelerator.

[0195] The thickness of a bleedout preventing layer is 1-10 μm and
preferably 2-7 μm, in view of in view of improving the heat resistance
of a substrate, making it easy to adjust the balance in the optical
property of a substrate, and preventing the curl of a smooth film when a
bleedout preventing layer is provided only on one surface of a substrate.

<<Use Application of Gas Barrier Film>>

[0196] The use application of the gas barrier film of the present
invention will be explained.

[0197] The gas barrier film of the present invention may be used as
varieties of matetials or films for sealing.

[0198] The gas barrier film of the present invention can be used
specifically usefully for an organic photoelectric conversion element.
Since the gas barrier film of the present invention is transparent, when
used for an organic photoelectric conversion element, this gas barrier
film can be used as a substrate and the element can be constructed so
that sun light is introduced from this side. Namely, a transparent
conductive layer such as an ITO layer can be provided as a transparent
electrode to construct a resin substrate for an organic photoelectric
conversion element.

[0199] An organic photoelectric conversion element can be sealed off by:
forming a semiconductor layer on an ITO transparent conductive layer use
as an electrode provided on a substrate; providing an electrode
constituted of a metal layer to form an organic photoelectric conversion
element; and laminating another sealing material (which may be the same
as the above gas barrier film), followed by adhering the aforementioned
gas barrier film substrate and the peripheral to seal off the element,
whereby an adverse affect of the outside moisture or oxygen gas to the
element can be prevented.

[0200] The resin substrate for an organic photoelectric conversion element
is obtained by forming a transparent conductive film on the layer which
has silicon and oxygen of thus obtained gas barrier film.

[0201] Formation of a transparent conductive film can be conducted by
using, for example, a vacuum evaporation method or a sputtering method.
It can also be formed via a coating method, for example, by employing a
sol-gel method using, for example, alkoxides of indium and tin. The
thickness of a transparent conductive film is preferably 0.1 nm-1000 nm.

[0202] Subsequently, an organic photoelectric conversion element which is
one of the preferable desirable uses of the gas barrier film of the
present invention will be explained.

<<Organic Photoelectric Conversion Element>>

[0203] The organic photoelectric conversion element of the present
invention will be explained.

[0204] Regarding the gas barrier film of the present invention, on the
outermost surface of the gas barrier layer, a transparent conductive
layer is further formed as an anode, a layer constructing an organic
photoelectric conversion element is formed on the anode, a layer to be a
cathode is laminated, and another gas barrier film is laminated thereon
as a sealing film, followed by adhering.

[0205] As another sealing material (a sealing film), a gas barrier film
having a layer containing the inorganic compound having the
aforementioned dense structure can be employed. Also, a gas barrier film
known in the art, for example, used as a wrapping material, such as a
plastic film vacuum evaporated thereon silicon oxide or aluminum oxide,
and a gas barrier film having a constitution in which dense ceramic layer
and shock relaxing polymer layers having flexibility are alternatively
laminated, may be used as the sealing film.

[0206] Specifically, a metal foil on which resin laminate (a polymer
layer) is formed is preferably used as a scaling film for a purpose in
which ejection of light is not expected (transparency is not required),
although it cannot be used as a gas barrier film on the light ejecting
side.

[0207] In the present invention, a metal foil means a foil or a film of a
metal produced, for example, by rolling, and it is distinguished from a
thin film of a metal formed via sputtering or vacuum evaporation, or from
an electrically conductive film formed from a fluid electrode material
such as an electrically conductive paste.

[0208] The metal element of a metal foil is not specifically limited, and
cited may be a copper (Cu) foil, an aluminum (Al) foil, a gold (Au) foil,
a brass foil, a nickel (Ni) foil, a titanium (Ti) foil, a copper alloy
foil, a stainless steel foil, a tin (Sn) Foil and a high
nickel-content-alloy foil. Among these various metal foils, an aluminum
foil may be cited as a specifically preferable metal foil.

[0209] The thickness of a metal foil is preferably 6-50 μm, in view of
preventing occurrence of pin holes, improving a gas barrier property
(namely, a moisture permeability or an oxygen permeability), and
improving the productivity

[0210] In a metal foil laminated with a resin film (a polymer film)
laminated thereon, the various materials desctived in "KINOUSEI
HOUSOUZAIRYO NO SHINTENKAI" (published by Toray Research Center, Inc.)
may be used for the resin film, examples of which include: a polyethylene
resin, a polypropylene resin, a polyethylene terephthalate resin, a
polyamide resin, an ethylene-vinyl alcohol copolymer resin, an
ethylene-vinyl acetate copolymer resin, an acrylonitrile-butadiene
copolymer resin, a cellophane resin, a vinylon resin and a vinylidene
chloride resin.

[0211] Resins such as a polypropylene resin and a nylon resin may be
stretched, or, further, may be coated with a vinylidene chloride resin.
With respect to a polyethylene resin, a low density resin or a high
density resin may be used.

[0212] Although will be mentioned later, as a method to seal two films,
for example, a resin layer which can be thermally fused using a commonly
used impulse sealer is laminated, and sealed using an impulse sealer by
fusing. In this case, the thickness of a gas barrier film is preferably
300 μm or less, in view of improving the handling property of the film
in the sealing process, and easier thermal fusion, for example, when an
impulse sealer is used.

(Seal of Organic Photoelectric Conversion Element)

[0213] In the organic photoelectric conversion element of the present
invention, the organic photoelectric conversion element can be sealed off
by: forming each layer of an organic photoelectric conversion element on
a resin substrate for an organic photoelectric conversion element
obtained by forming a transparent conductive layer on the gas barrier
film of the present invention; and covering the cathode surface with the
aforementioned sealing film under a purged circumstance with an inert
gas.

[0214] As an inert gas, a rare gas such as He or Ar is preferably used
besides N2. A rare gas obtained by mixing He and Ar is also
preferably used. The ratio of a rare gas in the gas phase is preferably
90-99.9% by volume. The storage stability of the organic photoelectric
conversion element is improved by sealing under a purged circumstance
with an inert gas.

[0215] When an organic photoelectric conversion element is sealed using
the aforementioned metal foil laminated with a resin film (a polymer
layer), it is preferable that a ceramic layer is formed on a metal foil,
and the surface of the layer containing the ceramic compound is adhered
onto the cathode, but not the surface of the resin film laminated on the
metal foil.

[0216] When the polymer layer side is adhered onto the cathode, it may
occasionally happen that electrical conduction partially occurs.

[0217] As the method to adhere a sealing film onto the cathode of an
organic photoelectric conversion element, cited may be a method to
laminate a film which is commonly used and can be thermally fused using
an impulse sealer, for example, an ethylene-vinyl acetate copolymer (EVA)
film, a polypropylene (PP) film or a polyethylene (PE) film, followed by
sealing using an impulse sealer by fusing.

[0218] As an adhesion method, a dry lamination method is excellent in view
of workability. In this method, a curable adhesives layer of about
1.0-2.5 μm thick is generally used.

[0219] However, since the adhesive may tunnel, bleed out or cause wrinkles
by shrinking when the applied amount of the adhesive is too much, the
applied amount of the adhesive is preferably adjusted within 3-5 μm as
a dried film.

[0220] A hot melt lamination method is a method to melt a hot melt
adhesive agent and apply onto a substrate to form an adhesive layer. In
this method, the thickness of the adhesive layer can be selected in a
wide range of 1-50 μm. As a base resin of a generally used hot melt
adhesive agent, for example, EVA, EEA, polyethylene, and butyl rubber are
usable. Also, for example, rosin, a xylene resin, a terpene resin or a
stylene resin is used as an adhesiveness providing agent, and, for
example, a wax is used as a plasticizer.

[0221] The extrusion lamination method represents a method to apply a
resin melted at a high temperature onto a substrate using a die. In this
method, it is possible to select the thickness of the resin layer within
a wide range of 10-50 μm.

[0222] As a resin used for the extrusion lamination method, for example,
LDPE, EVA and PP are generally usable.

[0223] Subsequently, the layer constitution of the organic photoelectric
conversion element of the present invention will be explained.

(Constitution of Organic Photoelectric Conversion Element)

[0224] Preferable embodiments of an organic photoelectric conversion
element relating the present invention will be explained, however, the
present invention is not limited thereto.

[0225] The constitution of the organic photoelectric conversion element of
the present invention is not specifically limited, and it is preferably
an element which has an anode, a cathode and at least one electric power
generation layer (a mixed layer of a p-type semiconductor and an n-type
semiconductor, also referred to as a bulk hetrojunction layer or an i
layer), and generates electricity when irradiated with light.

[0232] The power generation layer of the organic photoelectric conversion
element of the present invention will be explained.

[0233] The power generation layer of the organic photoelectric conversion
element of the present invention needs to contain a p-type semiconductor
material which can convey an electron hole, and an n-type semiconductor
material which can convey an electron. These materials may form a
heterojunction with substantially two layers or may form a bulk
heterojunction with one layer inside of which is of a mixed state, while
the bulk heterojunction is preferred in view of a improving the
photoelectric conversion efficiency.

[0234] The p-type semiconductor material and the n-type semiconductor
material will be described later.

[0235] As the same as the case of the emission layer of an organic EL
element, the efficiency of taking out holes and electrons from the
anode•cathode, respectively, can be improved by sandwiching the
power generation layer with a hole transport layer and an electron
transport layer. Accordingly, the constitutions having those (namely,
(ii) and (iii)) are more preferable.

[0236] The power generation layer itself may also be of a constitution in
which the power generation layer is sandwiched between a layer containing
a p-type semiconductor material and a layer containing an n-type
semiconductor material as shown in (iv) (also referred to as p-i-n
constitution) in order to improve the rectification property of holes and
electrons (namely, selectivity of carriers taken out).

[0237] Further, in order to improve the utilization efficiency of the
sunlight, it may be of a tandem constitution (namely, the constitution
shown as (v)) in which sun light of different wavelength can be absorbed
by respective power generation layers.

[0238] In order to raise the utilization rate of sunlight (or a
photoelectric conversion efficiency), it is also possible to adopt a
constitution of a back contact type organic photoelectric conversion
element in which Positive hole transport layer 14 and Electron transport
layer 16 are respectively formed on a pair of comb electrodes and further
a Photoelectric conversion part 15 is arranged thereon, instead of the
sandwich structure as shown in FIG. 1.

[0239] Further, detailed preferable embodiments of the organic
photoelectric conversion elements of the present invention will be
explained with referring to FIGS. 1-3.

[0241] Substrate 11 is a member which holds Anode 12, Power generation
layer 14, and Cathode 13 which are laminated successively. In this
embodiment, light to be photoelectrically converted enters from the side
of Substrate 11. Accordingly, Substrate 11 is a member which can transmit
light to be photoelectrically converted, namely, a transparent member
with respect to the light to be photoelectrically converted.

[0242] As Substrate 11, for example, a glass substrate or a resin
substrate is used. Substrate 11 is not always necessary and organic bulk
heterojunction type Organic photoelectric conversion element 10 may be
constituted by forming Anode 12 and Cathode 13 on both sides of Power
generation layer 14, for example.

[0243] The power generation layer 14 is a layer which converts light
energy to electric energy, and is constituted of a bulk heterojunction
layer in which a p-type semiconductor material and an n-type
semiconductor material are uniformly mixed. A p-type semiconductor
material functions as a relatively electron donating material (or a
donor), and an n-type semiconductor material functions as a relatively
electron accepting material (or an acceptor).

[0244] In FIG. 1, the incident light entering to Anode 12 through
Substrate 11 is absorbed by an electron donor or an electron acceptor in
the bulk heterojunction layer of Photoelectric conversion layer 14. An
electron is transferred from the electron donor to the electron acceptor
to form a pair of electron and positive hole (charge separation state).

[0245] The generated electric charge is transported by an internal
electric field, for example, the electric potential difference of Anode
12 and Cathode 13 when the work functions of Anode 12 and Cathode 13 are
different. An electron passes through electron acceptors, while a
positive hole passes through electron donors, and the electron and the
positive hole each are respectively transported to a different electrode,
and a photocurrent is detected.

[0246] For example, when the work function of Anode 12 is larger than the
work function of Cathode 13, the electron is transported to Anode 12 and
the positive hole is transported to Cathode 13.

[0247] In addition, if the size of a work function is reversed, the
electron and the positive hole will be transported to the reverse
direction to that described above. Moreover, the transportation
directions of an electron and a positive hole are also controllable by
applying a potential between Anode 12 and Cathode 13.

[0248] In addition, although not described in FIG. 1, it may be possible
to have other layers, such as a positive hole block layer, an electron
block layer, an electron injection layer, a positive hole injection
layer, or a smoothing layer.

[0249] More preferable structure is a structure in which the
above-mentioned Power generation layer 14 is composed of three layered
structure of so-called p-i-n structure (FIG. 2). The usual bulk
heterojunction layer is a single layer i containing a p-type
semiconductor material and an n-type semiconductor material mixed with
each other. By sandwiching the i layer with a p layer composed of a
p-type semiconductor material single substance and an n layer composed of
an n-type semiconductor material single substance, the rectifying
property of a positive hole and an electron becomes higher, the loss
caused by the recombination of a positive hole and an electron which
carried out charge separation is reduced, and still higher photoelectric
conversion efficiency can be acquired by this structure.

[0250] Furthermore, it is also possible to make a tandem type structure
produced by laminating a plurality of the aforesaid photoelectric
conversion elements for the purpose of improving a sunlight utilization
factor (photoelectric conversion efficiency).

[0251] FIG. 3 is a cross-sectional view showing a solar cell having an
organic photoelectric conversion element containing bulk heterojunction
layers of a tandem type. A tandem type structure can be made as follows.
After laminating Anode 12 and the First power generation layer 14'
successively on Substrate 11, Charge recombination layer 15 is laminated.
Then, Second power generation layer 16 and Counter electrode 13 are
laminated to achieve a tandem type structure. Second power generation
layer 16 may be a layer which absorbs the same spectrum as an absorption
spectrum of First power generation layer 14', or it may be a layer which
absorbs a different spectrum, however, it is preferably a layer which
absorbs a different spectrum. Moreover, both First power generation layer
14' and Second power generation layer 16 may be of the three layered
lamination structure of p-i-n as mentioned above.

<<P-Type Semiconductor Material, N-Type Semiconductor
Material>>

[0252] Materials used for forming the power generation layer (also
referred to as a photoelectric conversion layer) of the organic
photoelectric conversion element of the present invention will be
explained.

(P-Type Semiconductor Material)

[0253] As a p-type semiconductor material used for forming the bulk
heterojunction layer used as a power generation layer of the organic
photoelectric conversion element of the present invention, various types
of condensed polycyclic aromatic low molecular weight compounds and
conjugated polymers and oligomers are cited.

[0258] Among these, preferred are compounds which has a sufficient high
solubility to an organic solvent to be able to carry out a solution
process, and which forms a crystalline thin film and can realize a high
mobility after drying.

[0259] When an electron transporting layer is formed on a power generation
layer with a coating method, since there may occur the problem that the
solution for the electron transporting layer may dissolve the power
generation layer, it can be used a material which will become insoluble
after forming a layer with a solution process.

[0260] Examples of such materials include: a polythiophene compound having
a polymerizable group which becomes insoluble through cross-linked
polymerization after being coated as described in Technical Digest of the
International PVSEC-17, Fukuoka, Japan, 2007, p. 1225; a compound having
a soluble group which becomes insoluble (becomes to a pigment) by
addition of thermal energy as described in US 2003/136964 and JP-A No.
2008-16834.

(N-Type Semiconductor Material)

[0261] There is no limitation in particular to an n-type semiconductor
material used in the bulk heterojunction layer. Examples of such an
n-type semiconductor material include: fullerene, octaazaporphyrin, a
perfluoro compound of a p-type semiconductor, of which hydrogen atoms are
replaced with fluorine atoms (for example, perfluoropentacene and
perfluorophthalocyanine), a polymer compound which contains an aromatic
carboxylic acid anhydride and its imide in the structure, such as
naphthalenetetracarboxylic anhydride, naphthalenetetracarboxylic diimide,
perylenetetracarboxylic anhydride, and perylenetetracarboxylic diimide.

[0262] However, preferred is a fullerene derivative which enables high
speed (around 50 fs) and effective charge separation with varieties of
p-type semiconductor materials. Examples of a fullerene derivative
include: fullerene C60, fullerene C70, fullerene C76,
fullerene C78, fullerene C84, fullerene C240, fullerene
C540, mixed fullerene, fullerene nano-tube, multi layer nano-tube,
mono layer nano-tube, and nano-horn (cone type) and a fullerene
derivative a part of which is substituted with a hydrogen atom, a halogen
atom, a substituted or unsubstituted alkyl group, an alkenyl group, an
alkynyl group, an aryl group, a heteroaryl group, a cycloalkyl group, a
silyl group, an ether group, a thioether group, an amino group or a silyl
group.

[0264] Organic photoelectric conversion element 10 of the present
invention preferably has Positive hole transport layer 17 between the
bulk heterojunction layer and the anode, since it becomes possible to
more effectively take out charges generated in the bulk heterojunction
layer.

[0265] As a material to constitute the aforesaid layers, there can be used
for Positive hole transport layer 17, for example: PEDOT (product name
Baytron® made by Starck Vitec Co.), polyaniline and its dope material,
and a cyan compound described in WO 06/019270.

[0266] In addition, to the positive hole transport layer which has a LUMO
level shallower than the LUMO level of the n-type semiconductor material
used for a bulk heterojunction layer, there is provided an electron
blocking function having an rectifying effect by which the electron
generated in the bulk heterojunction layer is not passed to the anode
side.

[0267] The above-described positive hole transport layer is also called an
electron blocking layer, and it is more preferable to use a positive hole
transport layer having such function. Examples of these materials
include: a triaryl amine compound described in JP-A No. 5-271166, a metal
oxide such as molybdenum oxide, nickel oxide and tungsten oxide.

[0268] Moreover, the layer which consists of a single substance of a
p-type semiconductor material used for the bulk heterojunction layer can
also be used. As a means to form these layers, although any one of a
vacuum deposition method and a solution coating method can be used,
preferably used is a solution coating method. When a coated layer is
formed as an under layer before forming a bulk heterojunction layer, it
will have an effect of leveling the coating surface. This will result in
decreasing a leaking effect and it is preferable.

(Electron Transport Layer•Positive Hole Blocking Layer)

[0269] Organic photoelectric conversion element 10 of the present
invention preferably has Electron transport layer 18 between the bulk
heterojunction layer and the cathode, since it becomes possible to more
effectively take out charges generated in the bulk heterojunction layer.

[0270] As Electron transport layer 18, there can be used: octaazaporphyrin
and perfluoro derivative of a p-type semiconductor (for example,
perfluoro pentacene and perfluoro phthalocyanine). To the electron
transport layer which has a HOMO level deeper than the HOMO level of the
p-type semiconductor material used for a bulk heterojunction layer, there
is provided, at the same time, a positive hole blocking function having
an rectifying effect by which the positive hole generated in the bulk
heterojunction layer is not passed to the cathode side.

[0271] The above-described electron transport layer is also called as a
hole block layer, and it is more preferable to use the electron transport
layer which have such function.

[0272] Examples of a material for that include: a phenanthrene system
compound such as bathocuproine; an n-type semiconductor material such as
naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic
acid diimide, perylenetetracarboxylic acid anhydride and
perylenetetracarboxylic acid diimide; an n-type inorganic oxide such as
titanium oxide, zinc oxide and gallium oxide; and an alkali metal
compound such as lithium fluoride, sodium fluoride and cesium fluoride.

[0273] Moreover, the layer which consists of a single substance of an
n-type semiconductor material used for the bulk heterojunction layer can
also be used. As a means to form these layers, although any one of a
vacuum deposition method and a solution coating method can be used,
preferably used is the solution coating method.

(Other Layers)

[0274] It is also preferable to have a constitution containing various
interlayers in an element for the purpose of improvement in energy
conversion efficiency, and improvement in lifetime of the element.
Examples of an interlayer include: a positive hole blocking layer, an
electron blocking layer, a positive hole injection layer, an electron
injection layer, an exciton blocking layer, a UV absorption layer, a
light reflection layer and a wavelength conversion layer.

(Transparent Electrode (First Electrode))

[0275] A transparent electrode according to the present invention can be
selected according to the constitution of the element without
specifically limiting as a cathode or an anode, however, it is preferable
that a transparent electrode is used as an anode. For example, when the
transparent electrode is used as an anode, it is preferably an electrode
which transmits light of 380 to 800 nm. Examples of a material used for
that include: a transparent conductive metal oxide such as indium tin
oxide (ITO), SnO2 and ZnO; a metal thin film such as gold, silver
and platinum; a metal nanowire; and a carbon nanotube.

[0276] Usable is a conductive polymer selected from the group of
derivatives of: polypyrrole, polyaniline, polythiophene, poly thienylene
vinylene, polyazulene, polyisothianaphthene, polycarbazole,
polyacethylene, polyphenylene, polyphenylene vinylene, polyacene,
polyphenyl acetylene, polydiacetylene, and polynaphthalene. A transparent
electrode can also be constructed by combining a plurality of these
conductive compounds.

(Counter Electrode (Second Electrode))

[0277] A counter electrode may be a sole layer of a conductive material,
however, in addition to the conductive material, a resin may also be
added in combination to hold the conductive material. As a conductive
material for the counter electrode, a metal, an alloy, and an electric
conductive compound, having a small work function, and a mixture thereof
are usable.

[0279] Among these, from the viewpoints of a taking out property of an
electron and resistance to oxidation, preferable is a mixture of these
metals and the second metal which has a larger work function and is more
stable than these metals, for example, a magnesium/silver mixture, a
magnesium/aluminum mixture, a magnesium/indium mixture, an
aluminum/aluminum oxide (Al2O3) mixture, a lithium/aluminum
mixture, and aluminum.

[0280] The counter electrode can be produces by forming a thin film by
using a method such as vacuum evaporation or sputtering of the electrode
material. The thickness of the thin film is generally selected from 10 nm
to 5 μm, and preferably it is selected from 50 to 200 nm.

[0281] When a metallic material is used as a conductive material for a
counter electrode, the light arrived at the counter electrode side is
reflected and it is reflected to the first electrode side. This light
becomes possible to be recycled, and it is again absorbed by a
photoelectric conversion layer. This is preferable because this results
in more improvement of its photoelectric conversion efficiency.

[0282] Counter electrode 13 may be made of: a metal (for example, gold,
silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium and
indium), nanoparticles made of carbon, nanowires and a nano structure. A
dispersion of nanowires is preferable, since it can form a transparent
counter electrode having high electrical conductivity via a coating
method.

[0283] When the counter electrode side is made light transmissive, it can
be made as follows. After producing a film of a conductive material
suitable for a counter electrode, for example, an aluminum and an
aluminum alloy, silver, and a silver compound, having a thickness of
about 1 to 20 nm, a trans parent counter electrode can be produced by
providing a film of a conductive light transmissive material cited for
the description of the above-mentioned transparent electrode.

(Intermediate Electrode)

[0284] As a material for an intermediate electrode which is needed in a
tandem constitution as shown in the above-mentioned (v) (or in FIG. 3),
preferable is a layer using the compound having both transparency and
electrical conductivity. Materials used for the above-mentioned
transparent electrode are usable (a transparent metal oxide such as ITO,
AZO, FTO or titanium oxide; a very thin metal layers made of such as Ag,
Al and Au; a layer containing nanoparticles and nanowires; a conductive
polymer material such as PEDOT: PSS and poly aniline).

[0285] In addition, among the aforementioned positive hole transport layer
and electron transport layer, there may be a combination which be used as
an intermediate electrode (electric charge recombination layer) when they
are suitable selected and laminated with each other. When such
constitution is employed, it is preferable since one manufacturing
process to form one layer can be eliminated.

(Metal Nanowire)

[0286] As a conductive fiber according to the present invention, usable
are, for example, an organic or inorganic fiber which is coated with a
metal, a conductive metal oxide fiber, a metal nanowire, a carbon fiber
and a carbon nanotube. Among them, a metal nanowire is preferably used.

[0287] Generally, a metal nanowire indicates a linear structure composed
of a metallic element as a main structural element. In particular, the
metal nanowire in the present invention indicates a linear structure
having a diameter of a nanometer (nm) size.

[0288] In order to form a long conductive path by one metal nanowire and
to provide an appropriate light scattering property, a metal nanowire
according to the present invention is preferably have an average length
of 3 μm or more, more preferably 3 to 500 μm, and still more
preferably 3 to 300 μm. In addition, the relative standard deviation
of the length of the conductive fibers is preferably 40% or less.

[0289] Moreover, from a viewpoint of transparency, the average diameter is
preferably smaller. On the other hand, the average diameter is preferably
larger in view of the electrical conductivity. In the present invention,
the average diameter of a metal nanowire is preferably from 10 nm to 300
nm, and more preferably from 30 nm to 200 nm. Further, the relative
standard deviation of the diameter is preferably 20% or less.

[0290] There is no restriction in particular to the metal composition of
the metal nanowire according to the present invention, and it can be
composed of one sort or two or more sorts of metals of noble metal
elements or base metal elements. It is preferable that it contains at
least one sort of metal selected from the group of noble metals (for
example, gold, platinum, silver, palladium, rhodium, iridium, ruthenium
and osmium), iron, cobalt, copper and tin. It is preferable that at least
silver is included in it from a conductive viewpoint.

[0291] Moreover, for the purpose of achieving compatibility of
conductivity and stability (sulfuration resistance and oxidation
resistance of metal nanowire and migration resistance of metal nanowire),
it is also preferable that it contains silver and at least one sort of
metal belonging to the noble metal except silver. When the metal nanowire
of the present invention contains two or more kinds of metallic elements,
metal composition may be different between the surface and the inside of
metal nanowire, or the whole metal nanowire may have the same metal
composition.

[0292] In the present invention, there is no limitation in particular to
the production means of a metal nanowire. It is possible to prepare metal
nanowires via various methods such as a liquid phase method or a gas
phase method.

[0293] For example, the manufacturing method of an Ag nanowire may be
referred to Adv. Mater. 2002, 14, 833-837 and Chem. Mater. 2002, 14,
4736-4745; the manufacturing method of an Au nanowire may be referred to
JP-A No. 2006-233252; the manufacturing method of a Cu nanowire may be
referred to JP-A No. 2002-266007; and the manufacturing method of a Co
nanowire may be referred to JP-A No. 2004-149871.

[0294] Specifically, the manufacturing methods of Ag nanowires, described
in aforementioned Adv. Mater. and Chem. Mater., may be preferably
employed as a manufacturing method of a metal nanowire according to the
present invention, since via those methods, it is possible to simply
prepare a large amount of an Ag nanowire in an aqueous system and the
electrical conductivity of silver is highest of all metals.

[0295] In the present invention, a three-dimensional conductive network is
formed by mutual contact of nanowires and high conductivity is achieved.
By this, a light can penetrate the window part of the conductive network
where metal nanowires do not exist, and further, it becomes possible to
perform efficiently the generation of electricity by the scattering
effect of the metal nanowires in the organic photoelectric conversion
layer portion. It is a preferable embodiment to arrange a metal nanowire
in a portion closer to the organic power generation region in the first
electrode because the light scattering effect of the metal nanowire can
be effectively utilized.

(Optical Function Layer)

[0296] The organic photoelectric conversion element of the present
invention may be provided with various types of optical function layers
for the purpose of efficient light receiving of sunlight. As an optical
function layer, there may be provided an anti-reflection layer, a light
condensing layer such as a microlens array, a light diffusion layer which
can scatter the light reflected by the cathode and can make the light
enter again in the photoelectric conversion layer.

[0297] As an anti-reflection layer, well-known anti-reflection layer can
be prepared. For example, when a transparent resin film is a biaxial
stretching polyethylene terephthalate film, it is preferable to set the
refractive index of the adhesion assisting layer, which is adjacent to
the film, to be from 1.57 to 1.63. This will improve transmittance by
decreasing the interface reflection between the film substrate and the
adhesion assisting layer.

[0298] As a way of adjusting a refractive index, it can be carried out by
adjusting suitably the ratio of a binder resin to oxide sol having a
comparatively high refractive index such as a tin oxide sol and a cerium
oxide sol and by coating it. Although a single layer of adhesion
assisting layer may be sufficient, in order to raise adhesion property, a
composition of two or more adhesion assisting layers may also be used.

[0299] Regarding the light condensing layer, it is possible to increase an
amount of the receiving light from a special direction or, conversely, to
reduce the incident angle dependency of sunlight by providing a structure
of a micro lens array on the sunlight receiving side of the substrate or
by using in combination with a so-called light condensing sheet.

[0300] As an example of a microlens array, it can be cited an arrangement
in which the quadrangular pyramidal forms having a base of 30 μm and a
vertex angle of 90 degrees are two-dimensionally arranged on the light
taking out side of a substrate. The base is preferably in the range of 10
μm to 100 μm. When it is smaller than this range, the effect of
diffraction will occur to result in coloring, while when it is larger
than this range, the thickness becomes large, whereby it is not
desirable.

[0301] Moreover, as a light scattering layer, a various types of
anti-glare layers and a layer in which are distributed nanoparticles or
nanowire made of metal or various inorganic oxides in a colorless
transparent polymer can be cited.

(Film Formation Method and Surface Treatment Method)

[0302] As a formation method of a bulk heterojunction layer in which an
electron acceptor and an electron donor are mixed, a transport layers and
electrodes, a vacuum evaporation method and a coating method (including a
cast method and a spin coat method) may be cited. Of these, as a
formation method of a bulk heterojunction layer, a vacuum evaporation
method and a coating method (including a cast method and a spin coat
method) may be cited.

[0303] Among these, a coating method is preferable in order to increase
the area of the interface which carries out charge separation of the
above-mentioned positive hole and electron and to produce an element
having high photoelectric conversion efficiency. Moreover, the coating
method is excellent also in production velocity.

[0304] Although there is no limitation in the coating method to be used,
examples of the methods are cited as: a spin coat method, a cast method
from a solution, a dip coat method, a blade coat method, a wire bar coat
method, a gravure coat method and a spray coat method. In addition, also
applicable is the pattering method using printing methods such as: an
ink-jet method, a screen printing method, a typographic printing method,
an intaglio printing method, an offset printing method and a flexography
method.

[0305] After coating, it is preferable to heat the film in order to remove
the residual solvent, water and a gas, as well as to improve the mobility
and to shift the absorption in the longer wavelength due to
crystallization of a semiconductor material. When an annealing treatment
is carried out at a prescribed temperature during a manufacturing
process, aggregation or crystallization is microscopically promoted and a
suitable phase separation structure can be made in a bulk heterojunction
layer. As a result, the carrier mobility of a bulk heterojunction layer
can be improved and high efficiency can be obtained.

[0306] Power generation layer (Bulk heterojunction layer) 14 may be a
single layer containing a uniform mixture of an electron acceptor and an
electron donor. It may be a multiplicity of layers each having a
different mixing ratio of an electron acceptor and an electron donor. In
this case, it becomes possible to form the layer using an aforementioned
material which becomes insoluble after coating.

(Patterning)

[0307] There is no limitation in particular in the method and the process
of patterning, for example, an electrode, a power generation layer, a
positive hole transport layer and an electron transport layer according
to the present invention, and a well-known approach can be applied
suitably.

[0308] In the case of a soluble material used for a bulk heterojunction
layer and a transport layer, only a unnecessary part may be wiped off
after the complete application with a die coat, or a dip coat, or it may
be directly patterned at the time of an application using the methods
such as an ink-jet method or a screen printing method.

[0309] In the case of an insoluble material used for such as an electrode
material, mask deposition can be performed at the time of vacuum
deposition, or it can be patterned by the well-known methods such as
etching or lift-off. Moreover, it may also be possible to form a pattern
by transferring the pattern formed on another substrate.

[0310] Then, in order to confirm the inclination property of the wire and
the existence of a copper-zinc-nickel three component alloy plating, the
following measurement was carried out.

[0311] Measurement using XPS (X-ray photoelectron microscopy) the element
distribution (a concentration inclination) along the depth direction of a
wire of copper-zinc-nickel three component plating was investigated
before and after the final stretching via a wet method using the
instrument (the instrument is one in which routine of: the concentration
of element at the measurement surface of a sample is measured; the
measurement surface is scraped with an Ar gas; and the concentration of
the element at the newly appeared surface on the measuring surface
appeared by scraping is measured, is repeated, whereby the concentration
inclination of the element along the depth direction of the sample is
analyzed).

EXAMPLES

[0312] The present invention will be specifically explained with referring
to examples below, however, the present invention is not limited thereto.

Example 1

[0313] At first, Substrate 1 and Substrate 1a each were prepared.

<<Preparation of Substrate 1>>:

[0314] On one surface of a polyester film, a bleed out preventing layer
was formed and, on the other surface, a smooth layer was formed.

[0315] As the substrate of a thermoplastic layer, a polyester film having
a thickness of 125 μm (TETRON 03, produced by Teijin DuPont Films
Japan Limited), both surfaces of which were subjected to an
adhesion-enhancing treatment was annealed at 170° C. for 30
minutes to be used.

[0316] After a bleed out preventing layer was formed on one surface of the
polyester film and a smooth layer was formed on the other surface, an
adhesive protective layer was pasted, while the aforementioned polyester
film was conveyed at a speed of 30 m/minute, whereby a substrate of a
roll-like shape was obtained.

(Preparation of Bleed Out Preventing Layer)

[0317] On one surface of the a polyester film, a UV curable
organic/inorganic hybrid hard coat material OPSTAR Z7535 produced by JSR
Corp. was applied using a wire bar so that the thickness after dried was
4 μm, followed by conducting a hardening treatment under a hardening
condition: 1.0 J/cm2, in air, and using a high-pressure mercury
lamp, and a drying condition: 800° C. for 3 minutes. Thus, a bleed
out preventing layer was formed.

(Preparation of Smooth Layer)

[0318] Subsequently, on the other surface of the above polyester film, a
UV curable organic/inorganic hybrid hard coat material OPSTAR Z7501
produced by JSR Corp. was applied using a wire bar so that the thickness
after dried was 4 μm, followed by drying under a condition: 80°
C. for 3 minutes. Then, a hardening treatment was conducted in air using
a high-pressure mercury lamp under a hardening condition: 1.0 J/cm2.
Thus, a smooth layer was formed.

<<Preparation of Substrate 1a>>

[0319] Substrate 1a was prepared in the same manner as the preparation of
Substrate 1 except that, instead of the polyester film, a composite film
(having a thickness of 145 μm) obtained by pasting an aluminum foil
(also referred to as an aluminum-foil, one having a thickness of 20 μm
was used) and a polyester film with each other.

[0320] Subsequently, as described below, Gas barrier films 1, 3-13 and 17
of the present invention and comparative Gas barrier films 14-16 each
were prepared employing obtained Substrate 1, and Gas barrier film 2 of
the present invention was prepared employing Substrate 1a (where
Substrate 1a was a composite film obtained by pasting an aluminum foil
and a polyester film with each other).

[0321] The schematic cross-sectional view of each gas barrier film was
shown in FIG. 4 for the constitution of Gas barrier film 1 of the present
invention, FIG. 5 for the constitution of Gas barrier film 2 of the
present invention, FIG. 6 for the constitution of Gas barrier film 3 of
the present invention, FIG. 7 for the constitution of Gas barrier film 4
of the present invention, FIG. 8 for the constitution of Gas barrier
films 5-8 of the present invention, FIG. 9 for the constitution of Gas
barrier film 9 of the present invention, FIG. 10 for the constitution of
Gas barrier films 10 and 17 of the present invention, FIG. 11 for the
constitution of Gas barrier films 11, 12 and 13 of the present invention,
FIG. 12 for the constitution of comparative Gas barrier films 14 and 15,
and FIG. 13 for the constitution of comparative Gas barrier film 16.

[0322] With respect to each schematic cross-sectional view of the
constitution of the gas barrier film shown in FIGS. 4-13, Substrate 1 has
a bleed out preventing layer on one surface of the polyester film and a
smooth layer on the other surface. However, these layers are not
illustrated in FIGS. 4-13.

Manufacturing of Gas Barrier Film 1

[0323] The manufacturing of Gas barrier film 1 of the present invention
will be explained based on the cross-sectional view of the constitution
of Gas barrier film 1 shown in FIG. 4.

Process 1: Preparation of a PHPS Coated Film

[0324] On the smooth layer of the Substrate 1, the following PHPS
(perhydro polysilazane) solution was applied via a spin coat method (at
2000 rpm, for 60 seconds), and was dried for 10 minutes at 80° C.,
and thus a PHPS coated film (also referred to as merely a PHPS coatt
film) was obtained.

[0325] The obtained PHPS coat film (also referred to as a coated film) was
not the Silanol-containing layer 2 in this stage, and Silanol-containing
layer 2 was formed via a treatment in which the above mentioned PHPS coat
film was subjected to a treatment described as Process 3 (treated under
an environment of 60° C. and RH 90% for 3 hours).

(Preparation of PHPS Coating Liquid)

[0326] A 20 mass % dibutylether solution of perhydro polysilazane (PHPS)
(Aquamica NN120-20, non-catalyst type, produced by AZ Electronic
Materials) was diluted using dibutylether so as to obtain a 10 mass %
liquid.

Process 2: Preparation of Gas Barrier Layer 3

[0327] A PHPS liquid prepared by diluting aforementioned NN120-20
(non-catalyst type) using dibutyl ether so as to obtain a 4 mass % liquid
was applied on the obtained PHPS coated film via a spin coat method (at
5000 rpm, for 60 seconds) to carry out stack coating on the PHPS coated
film, followed by drying at 80° C. for 10 minutes, and conducting
a UV ozone oxidation treatment for 30 minutes at 150° C. (a low
pressure mercury lamp was used as a light source).

[0328] Thus, Gas barrier layer 3 (having a thickness of 60 nm) containing
a silicon oxide layer which was converted from the polysilazane (also
mentioned as being oxidized) was prepared.

Process 3: Preparation of Silanol-Containing Layer 2

[0329] Silanol-containing layer 2 (having a thickness of 200 nm) was
prepared from the PHPS (perhydco polysilazane) coated film prepared in
Process 1 by heat treating (storing for 3 hours under an environment of
60° C. and 90 RH %) Substrate 1 on which Gas barrier layer 3 was
formed.

[0330] Here, each thickness of Gas barrier layer 3 and Silanol-containing
layer 2 was determined from the cross-sectional photograph obtained by
using a TEM (a transmission electron microscope) after film production
after the film formation.

[0331] The relative SiOH ionic strength detected by the Tof-SIMS
measurement of Silanol-containing layer 2 after Gas barrier film 1 was
prepared was 1.0 (provided that the relative Si ionic strength was set to
1).

Manufacturing of Gas Barrier Film 2

[0332] The manufacturing of Gas barrier film 2 of the present invention
will be explained based on the cross-sectional view of the constitution
of Gas barrier film 2 shown in FIG. 5.

[0333] Gas barrier film 2 was manufactured in the same manner as the
manufacturing of Gas barrier film 1 except that, instead of Substrate 1,
Substrate 1a (which was a composite film obtained by pasting an aluminum
foil and a polyester film with each other) was used.

Manufacturing of Gas Barrier Film 3

[0334] The manufacturing of Gas barrier film 3 of the present invention
will be explained based on the cross-sectional view of the constitution
of Gas barrier film 3 shown in FIG. 6.

[0335] Gas barrier film 3 was manufactured in the same manner as the
manufacturing of Gas barrier film 1 except that Gas barrier layer 3a
(having a thickness of 60 nm) was prepared on Substrate 1 as a second gas
barrier layer before the preparation of the PHPS coated film, and, after
Gas barrier layer 3 (having a thickness of 60 nm) was formed on the PHPS
coated layer, Substrate 1a was heat treated (storing for 3 hours under an
environment of 60° C. and 90 RH %) to obtain Silanol-containing
layer 2 (having a thickness of 200 nm).

[0336] The relative SiOH ionic strength detected by the Tof-SIMS
measurement of Silanol-containing layer 2 of obtained Gas barrier film 3
was 0.8 (provided that the relative Si ionic strength was set to 1).

(Formation of Gas Barrier Layer 3a)

[0337] After mixing a 20 mass % solution of perhydro polysilazane (PHPS)
in dibutyl ether (Aquamica NAX120-20, amine-catalyst type, produced by AZ
Electronic Materials) with aforementioned NN120-20 (non-catalyst type) in
a ratio of 1:4, the resulting solution was diluted so as to obtain a 4
mass % solution using dibutyl ether.

[0338] This diluted PHPS liquid was applied on the substrate via a spin
coat method (at 5000 rpm, for 60 seconds), and, after drying at
80° C. for 10 minutes, the following plasma discharge treatment
was conducted. Thus, Gas barrier layer 3a (having a thickness of 60 nm)
containing a silicon oxide film which was converted from the polysilazane
(also mentioned as being oxidized) was prepared.

(Plasma Discharge Treatment)

[0339] The condition of the plasma discharge treatment used for preparing
the second Gas barrier layer 3a will be shown below.

[0340] The substrate temperature was kept at 120° C. during the
film formation.

[0341] The treatment was carried out using a roll-electrode type discharge
treatment apparatus. A plurality of rod-shaped electrodes each facing a
roll electrode were installed along the lateral direction of the
roll-film support, and a plasma treatment was carried out on the coated
surface by supplying a raw material and electric power to each electrode
portion, as will be described below.

[0342] Both of the opposed electrodes were coated with a dielectric
material of a thickness of 1 mm by ceramic thermal spraying. The distance
between the electrodes after coated with the dielectric material was set
to 1 mm.

[0343] The metal base material which was coated with the dielectric
material was of a jacket type made of stainless steel having a cooling
function with cooling water. The discharge was carried out while
controlling the electrode temperature with the cooling water.

[0344] A high frequency power source from OYO ELECTRIC Co., Ltd. (80 kHz)
and a high frequency power source from Pearl Kogyo Co., Ltd. (13.56 MHz)
were used as the power sources.

Discharge gas: N2 gas

[0345] Reactive gas: oxygen gas Power of low frequency side power source:
3 W/cm2 of 80 kHz wave Power of high frequency side power source: 11
W/cm2 of 13.56 MHz wave

[0346] The conveyance speed was controlled to obtain the above condition.
After the coated layers were dried, each sample was stored under an
environment of 23° C. and 20% RH for 1-5 hours before conduction
the plasma treatment.

Manufacturing of Gas Barrier Film 4

[0347] The manufacturing of Gas barrier film 4 of the present invention
will be explained based on the cross-sectional view of the constitution
of Gas barrier film 4 shown in FIG. 7.

[0348] Gas barrier film 4 was manufactured in the same manner as the
manufacturing of Gas barrier film 1 except that, instead of heat treating
(keeping for 3 hours under an environment of 60° C. and 90 RH %)
to form Silanol-containing layer 2, the same plasma discharge treatment
as preparing Gas barrier layer 3a which was formed as the second gas
barrier layer of Gas barrier film 3 was conducted to form
Silanol-containing layer 2a.

[0349] The plasma discharge treatment was conducted after the PHPS coated
layer was formed and before Gas barrier layer 3 was prepared.

[0350] The relative SiOH ionic strength detected by the Tof-SIMS
measurement of Silanol-containing layer 2a was 0.55 (provided that the
relative Si ionic strength was set to 1).

[0351] Further, it was found by Tof-SIMS that the content of a silanol
group existing in Silanol-containing layer 2a showed a concentration
gradient along the film depth direction in which the content of the
silanol group became larger from the Gas barrier layer 3 side to the
Substrate 1 side.

Manufacturing of Gas Barrier Film 5

[0352] The manufacturing of Gas barrier film 5 of the present invention
will be explained based on the cross-sectional view of the constitution
of Gas barrier film 5 shown in FIG. 8.

[0353] Gas barrier film 5 was manufactured in the same manner as the
manufacturing of Gas barrier film 4 except that Gas barrier layer 3a was
prepared on Substrate 1 as a second gas barrier layer similar to the
manufacturing of Gas barrier film 3.

[0354] The relative SiOH ionic strength detected by the Tof-SIMS
measurement of Silanol-containing layer 2a was 0.55 (provided that the
relative Si ionic strength was set to 1).

[0355] Further, it was found by Tof-SIMS that the content of a silanol
group existing in Silanol-containing layer 2a showed a concentration
gradient along the film depth direction in which the content of the
silanol group became larger from the Gas barrier layer 3 side to the
Substrate 1 side.

Manufacturing of Gas Barrier Film 6

[0356] The manufacturing of Gas barrier film 6 of the present invention
will be explained based on the cross-sectional view of the constitution
of Gas barrier film 6 shown in FIG. 8.

[0357] Gas barrier film 6 was manufactured in the same manner as the
manufacturing of Gas barrier film 5 except that, as a PHPS liquid to form
a silanol-containing layer, a solution obtained by mixing NAX120-20 with
NN120-20 (non-catalyst type) in a ratio of 1:4 was used instead of
NN120-20 (non-catalyst type).

[0358] The relative SiOH ionic strength detected by the Tof-SIMS
measurement of Silanol-containing layer 2a was 0.4 (provided that the
relative Si ionic strength was set to 1).

[0359] Further, it was found by Tof-SIMS that the content of a silanol
group existing in Silanol-containing layer 2a showed a concentration
gradient along the film depth direction in which the content of the
silanol group became larger from the Gas barrier layer 3 side to the
Substrate 1 side.

Manufacturing of Gas Barrier Film 7

[0360] The manufacturing of Gas barrier film 7 of the present invention
will be explained based on the cross-sectional view of the constitution
of Gas barrier film 7 shown in FIG. 8.

[0361] Gas barrier film 7 was manufactured in the same manner as the
manufacturing of Gas barrier film 6 except that a hydrogen gas was used
as a reactive gas for the plasma discharge treatment conducted to form
Silanol-containing layer 2a, instead of an oxygen gas.

[0362] The relative SiOH ionic strength detected by the Tof-SIMS
measurement of Silanol-containing layer 2a was 0.7 (provided that the
relative Si ionic strength was set to 1).

[0363] Further, it was found by Tof-SIMS that the content of a silanol
group existing in Silanol-containing layer 2a showed a concentration
gradient along the film depth direction in which the content of the
silanol group became larger from the Gas barrier layer 3 side to the
Substrate 1 side.

Manufacturing of Gas Barrier Film 8

[0364] The manufacturing of Gas barrier film 8 of the present invention
will be explained based on the cross-sectional view of the constitution
of Gas barrier film 8 shown in FIG. 8.

[0365] Gas barrier film 8 was manufactured in the same manner as the
manufacturing of Gas barrier film 6 except that NAX120-20 was used as a
PHPS liquid to form Silanol-containing layer 2a, instead of a solution
obtained by mixing NAX120-20 (amine-catalyst type) with NN120-20
(non-catalyst type) in a ratio of 1:4.

[0366] The relative SiOH ionic strength detected by the Tof-SIMS
measurement of Silanol-containing layer 2a was 0.02 (provided that the
relative Si ionic strength was set to 1).

[0367] Further, it was found by Tof-SIMS that the content of a silanol
group existing in Silanol-containing layer 2a showed a concentration
gradient along the film depth direction in which the content of the
silanol group became larger from the Gas barrier layer 3 side to the
Substrate 1 side.

Manufacturing of Gas Barrier Film 9

[0368] The manufacturing of Gas barrier film 9 of the present invention
will be explained based on the cross-sectional view of the constitution
of Gas barrier film 9 shown in FIG. 9.

(Preparation of Gas Barrier Layer 3a)

[0369] Gas barrier layer 3a was prepared on Substrate 1 in the same manner
as the preparation of Gas barrier layer 3a prepared as the second gas
barrier layer in the manufacturing process of Gas barrier film 3.

[0370] After forming one PHPS coated layer on the obtained Gas barrier
layer 3a (namely, applying a liquid prepared by diluting aforementioned
NN120-20 (non-catalyst type) using dibutyl ether so as to obtain a 10
mass % liquid via a spin coat method (at 2000 rpm, for 60 seconds),
followed by drying at 80° C. for 10 minutes), a UV ozone oxidation
treatment (a low pressure mercury lamp was used as a light source) was
conducted on the obtained PHPS coated layer at 1500° C. for 30
minutes, whereby Silanol-containing layer 2a was prepared, and,
simultaneously, the surface portion of the Silanol-containing layer 2a
was converted from the PHPS film (namely, a polysilazane layer) to a
silicon oxide layer to form Gas barrier layer 3 (having a thickness of 60
nm). The thickness of the obtained Silanol-containing layer 2a was 140
nm.

[0371] The relative SiOH ionic strength detected by the Tof-SIMS
measurement of Silanol-containing layer 2a was 0.35 (provided that the
relative Si ionic strength was set to 1).

[0372] Further, it was found by Tof-SIMS that the content of a silanol
group existing in Silanol-containing layer 2a showed a concentration
gradient along the film depth direction (namely, a concentration gradient
in which the content of the silanol group became larger from the surface
of Silanol-containing layer 2a to the Gas barrier 3 side).

[0373] Here, it was confirmed by using a sputtering method and an XPS
surface analysis in combination that Gas barrier layer 3 was provided at
the surface layer (also referred to as a surface portion) of
Silanol-containing layer 2a by converting the surface portion of
Silanol-containing layer 2a to a film containing a silicon oxide
(SiO2).

[0374] It was found that, when the atomic ratio was measured using an XPS
surface analysis while etching was conducted at a rate of 0.5 nm/minute
in the depth direction form the surface, provided that the outermost
surface was set to 0 nm, the ratio of Si:O was almost 1:2 (namely, a
silicon dioxide film: SiO2 film) in the region from the surface to
around 60 nm.

[0375] The XPS surface analyzer used for the surface analysis is not
specifically limited, and any type of instrument may be used. In the
present invention, ESCALAB-200R manufactured by VG Scientific, Ltd. was
used. Measurement was carried out employing Mg as an X-ray anode, and at
output power of 600 W (in which accelerating voltage was 15 kV and
emission current was 40 mA).

Manufacturing of Gas Barrier Film 10

[0376] The manufacturing of Gas barrier film 10 of the present invention
will be explained based on the cross-sectional view of the constitution
of Gas barrier film 10 shown in FIG. 10.

[0377] Gas barrier film 10 was manufactured in the same manner as the
manufacturing of Gas barrier film 9 except that, after two layers of
Silanol-containing layer 2a and Gas barrier layer 3 were simultaneously
prepared, Gas barrier layer 3b was prepared on Gas barrier layer 3,
without preparing Gas barrier layer 3a which was a second gas barrier
layer on Substrate 1. Gas barrier layer 3b was prepared in the same
manner as the preparation of Gas barrier layer 3 in Gas barrier film 1.

[0378] The relative SiOH ionic strength detected by the Tof-SIMS
measurement of Silanol-containing layer 2a was 0.45 (provided that the
relative Si ionic strength was set to 1).

Manufacturing of Gas Barrier Film 11

[0379] The manufacturing of Gas barrier film 11 of the present invention
will be explained based on the cross-sectional view of the constitution
of Gas barrier film 11 shown in FIG. 11.

[0380] Gas barrier film 11 was manufactured in the same manner as the
manufacturing of Gas barrier film 10 except that Gas barrier layer 3a
described in Gas barrier film 9 was provided on Substrate 1.

[0381] The relative SiOH ionic strength detected by the Tof-SIMS
measurement of Silanol-containing layer 2a was 0.35 (provided that the
relative Si ionic strength was set to 1).

Manufacturing of Gas Barrier Film 12

[0382] The manufacturing of Gas barrier film 12 of the present invention
will be explained based on the cross-sectional view of the constitution
of Gas barrier film 12 shown in FIG. 11.

[0383] Gas barrier film 12 was manufactured in the same manner as the
manufacturing of Gas barrier film 11 except that the oxidation treatment
of Silanol-containing layer 2 was conducted by using a Xe excimer lamp
(having a wavelength of 172 nm) instead of the UV ozone oxidation
treatment (in which the whole body of Substrate 1 and Gas barrier 3a was
irradiated with Xe excimer for 10 seconds).

Manufacturing of Gas Barrier Film 13

[0384] The manufacturing of Gas barrier film 13 of the present invention
will be explained based on the cross-sectional view of the constitution
of Gas barrier film 13 shown in FIG. 11.

[0385] Gas barrier film 13 was manufactured in the same mariner as the
manufacturing of Gas barrier film 11 except that Gas barrier layer 3b was
prepared by using a plasma discharge treatment (in which reactive gas was
oxygen) used in the manufacturing of Gas barrier film 3, instead of the
UV ozone oxidation treatment.

Manufacturing of Gas Barrier Film 14

Comparative Example

[0386] The manufacturing of comparative Gas barrier film 14 will be
explained based on the cross-sectional view of the constitution of Gas
barrier film 14 shown in FIG. 12.

[0387] Gas barrier film 13 was manufactured by applying a liquid prepared
by diluting NN120-20 (catalyst type) using dibutyl ether so as to obtain
a 10 mass % liquid via a spin coat method (at 2000 rpm, for 60 seconds)
on Substrate 1, and drying at 80° C. for 10 minutes, followed by
conducting a UV ozone oxidation treatment at 150° C. for 30
minutes.

[0388] It was confirmed by using the aforementioned XPS surface analysis
that all the polysilazane was converted to a silicon oxide film.

Manufacturing of Gas Barrier Film 15

Comparative Example

[0389] The manufacturing of comparative Gas barrier film 15 will be
explained based on the cross-sectional view of the constitution of Gas
barrier film 15 shown in FIG. 12.

[0390] Gas barrier film 15 having Gas barrier layer 3 on Substrate 1 was
manufactured in the same manner as the preparation of Gas barrier film 14
except that the treatment of Gas barrier layer 3 was carried our by
heating at 1500° C. for 30 minutes in air on a hot plate, instead
of the UV ozone oxidation treatment.

[0391] It was confirmed by using the aforementioned XPS surface analysis
that all the polysilazane was converted to a silicon oxide film.

Manufacturing of Gas Barrier Film 16

Comparative Example

[0392] The manufacturing of comparative Gas barrier film 16 will be
explained based on the cross-sectional view of the constitution of Gas
barrier film 16 shown in FIG. 13.

[0393] Comparative Gas barrier film 16 was manufactured in the same manner
as the preparation of Gas barrier film 1 except that the condition for
preparing Silanol-containing layer 2 from the PHPS coating liquid
described in Process 3 (storing for 3 hours under an environment of
60° C. and 90 RH %) was changed to storing for 15 hours.

[0394] The relative SiOH ionic strength detected by the Tof-SIMS
measurement of Silanol-containing layer 2 was 1.4 (provided that the
relative Si ionic strength was set to 1).

Manufacturing of Gas Barrier Film 17

[0395] The manufacturing of comparative Gas barrier film 17 will be
explained based on the cross-sectional view of the constitution of Gas
barrier film 17 shown in FIG. 10.

[0396] Gas barrier film 17 was manufactured in the same manner as the
manufacturing of Gas barrier film 10 except that, a solution obtained by
mixing NAX120-20 (amine catalyst type) with NN120-20 (non-catalyst type)
in a ratio of 1:4 was used as a PHPS liquid to form Silanol-containing
layer 2a, Gas barrier layer 3 and Gas barrier layer 3b, and the formation
of Gas barrier layer 3 on Silanol-containing layer 2a and Gas barrier
layer 3b on Gas barrier layer 3 was conducted by using a Xe excimer lamp
(having a wavelength of 172 nm) instead of a UV ozone treatment.

[0397] The excimer lamp irradiation condition in this preparation was as
follows. Using a stage movable type xenon excimer irradiation equipment
(production of MD excimer Inc., MECL-M-1-200), irradiation was carried
out at, the excimer light intensity: 130 mW/cm2 (172 nm), the
distance between the lamp of excimer light source and the substrate: 3
mm, the stage temperature: 100° C., the treatment environment:
under dry nitrogen atmosphere, the oxygen concentration in the treatment
atmosphere: 0.1%, the moving speed of the stage: 10 mm/second, and
conveyance: 10 times.

[0398] On each of the Gas barrier films 1-13 and 17 of the present
invention and comparative Gas barrier films 14-16, tests for water vapor
permeation rate and bending property were carried out as described below.

<<Measurement of Water Vapor Permeation Rate and Evaluation>>

[0399] The water vapor permeation rate which is an index of the gas
barrier property was measured as described below.

[0406] On the surface of gas barrier layer (also referred to as a ceramic
layer surface) of each of Gas barrier films 1 to 17, which had been
subjected to 100 times repeated bending treatment at an angle of
180° to form a curvature radius of 10 mm in advance, metallic
calcium was vacuum evaporated using a vacuum evaporation apparatus
(Vacuum evaporation apparatus JEE-400 produced by JEOL Co., Ltd.) on the
barrier film sample before a transparent conductive film was formed,
while masking other than the portions to be evaporated (9 portions of the
size 12 mm×12 mm).

[0407] After that, the mask was removed while the vacuum was maintained,
and aluminum was evaporated from another metal evaporation source onto
entire surface of one side. After the aluminum sealing, the vacuum state
was released, and, promptly, the aluminum sealed surface was faced with a
quartz glass plate having a thickness of 0.2 mm through a UV curable
resin for sealing (produced by Nagase ChemteX Corporation) under a dried
nitrogen atmosphere, followed by being irradiated with ultraviolet light.
The evaluation cells were thus prepared.

[0408] In order to confirm the change in gas barrier property before and
after the bending, evaluation cells for water vapor barrier property were
prepared also using gas barrier films which were not subjected to
bending.

[0409] The obtained samples were stored under a high temperature-high
humidity condition of 60° C. and 90% RH, and the amount of water
permeated into the cell was calculated from the amount of corrosion of
metallic calcium according to the method described in JP-A No.
2005-283561.

[0410] In order to confirm that there is no moisture permeation from a
surface other than the barrier film surface, a sample in which metallic
calcium was vacuum evaporated on a 0.2 mm thick quartz glass plated
instead of the barrier film was stored under the same high
temperature-high humidity condition of 600° C. and 90% RH, as a
comparative sample, to confirm that there was no corrosion of metallic
calcium even after 1000 hours.

[0411] The water vapor permeation rate of each of Gas barrier films 1 to
17 was evaluated in the following 5 stage ranks.

[0412] Obtained results were listed in Table 2.

5: less than 5×10-5 g/(m224 h) 4: 5×10-5
g/(m224 h) or more but less than 1×10-4 g/(m224 h)
3: 1×10-4 g/(m224 h) or more but less than
1×10-3 g/(m224 h) 2: 1×103 g/(m224 h) or
more but less than 1×10-2 g/(m224 h) 1: 1×10-2
g/(m224 h) or more

[0414] Each of Gas barrier films 1 to 17 was repeatedly bent 100 times at
an angle of 180° to form a curvature radius of 20 mmφ while
the surface having the gas barrier layer was on the outside.

[0415] Then, at the time of measurement of the water vapor permeation rate
which will be mentioned later, presence or non-presence of generation of
cracks was visually observed from the corrosion situation of metallic
calcium, and the ranking evaluation according to the following 3 stages
of ranks was conducted.

[0416] A: No corroded state looks as cracks was observed.

[0417] B: Corroded state looks as minute crack was observed.

[0418] C: Corroded state of a large area looks as obvious cracks was
observed.

[0419] Preparations of gas barrier layers and silanol-containing layers of
Gas barrier films 1 to 17 were listed in Tables 1 and 2, and
subsequently, the evaluation of the gas barrier properties (water vapor
permeation rates) and the bending endurances (also referred to as
cracking resistance) of Gas barrier films 1 to 17 were listed in
following Table 2.

[0420] It is clear from Tables 1 and 2 that, when compared with the
comparative Gas barrier films 14 to 16, each of Gas barrier films 1 to 13
and 17 of the present invention shows a high gas barrier property (a low
water vapor permeation rate), and an excellent bending endurance
(cracking resistance).

Example 2

[0421] Gas barrier films 1 to 17 each having been subjected to 50 times
repeated bending at an angle of 180° to form a curvature radius of
10 mm, and Gas barrier films 1 to 17 each having not been subjected to
the above bending were prepared, and, then, both Gas barrier films 1 to
17 each having a transparent conductive film described below were
prepared. Using Gas barrier films 1 to 17 each having been subjected the
bending treatment and Gas barrier films 1 to 17 each having not been
subjected to the bending treatment, each set of Organic photoelectric
conversion elements 1 to 17 were prepared.

<<Manufacturing of Gas Barrier Films 1 to 17 Having been Subjected
to Bending Treatment and Those Having not been Subjected to Bending
Treatment Each Having a Transparent Conductive Film>>

[0422] Using a plasma discharge apparatus having parallel plate type
electrodes, thin film formation was carried out by mounting each
transparent film between the electrodes and introducing a mixed gas.

[0423] The grounded electrode was prepared as follows: A stainless steel
plate of 200 mm×200 mm×2 mm was covered by a high density and
adhesive alumina thermal sprayed layer and coated with a solution
prepared by diluting tetramethoxysilane with ethyl acetate and dried.
And, then, the coated layer was cured by UV irradiation, whereby pinhole
filling treatment was conducted. Thus obtained surface of the dielectric
substance covering layer was polished for smoothing so that the maximum
surface roughness Rmax was made to 5 μm. Thus prepared electrode
was used.

[0424] The electric power applying electrode which was composed of a
square columnar hollow pipe made of pure titanium, which was covered with
the same dielectric material as that used for the grounded electrode, was
used. Plural electric power applying electrodes were prepared and placed
facing to the grounded electrode to form a discharging space.

[0425] As the electric source for generating plasma, employed was an
electric power of 5 W/cm2 at 13.56 MHz supplied by the high
frequency power source CF-5000-13M, manufactured by Pearl Industry Co.,
Ltd.

[0426] A mixed gas having the following composition was flowed between the
electrodes to make a plasma state. On each film of Gas barrier films 1 to
17 each having been subjected the bending treatment and Gas barrier films
1 to 17 each having not been subjected to the bending treatment, as
prepared in Example 1, a tin-doped indium oxide (ITO) layer having a
thickness 150 nm was formed using the plasma state. Thus, Gas barrier
films 1 to 17 (including both sets of having been subjected to the
bending treatment and having not been subjected to the bending treatment)
each having a transparent conductive film were prepared.

[0431] On each of Gas barrier films 1 to 17 (including both sets of having
been subjected to the bending treatment and having not been subjected to
the bending treatment) each having a transparent conductive film (having
a thickness of 150 nm and a sheet resistance of 10Ω/quadrature),
a first electrode was formed by patterning in 2 mm width using a usual
photolithography technique and wet etching.

[0432] The patterned first electrode (anode) was washed via sequential
steps of ultrasonic washing using a surfactant and ultra pure water and
ultrasonic washing using ultra pure water, followed by drying under a
nitrogen flow, and, finally, cleaned via ultraviolet/ozone cleaning.
Transparent substrates 1 to 17 of each set were thus obtained.

[0433] On each surface of obtained Transparent substrates 1 to 17 of each
set, Baytron P4083 (produced by Starck Vitec, Co.) was applied and then
dried to obtain a layer thickness of 30 nm, subsequently, the layer was
subjected to a heat treatment at 150° C. for 30 minutes to form a
positive hole transport layer.

[0434] After that, each substrate was carried into a nitrogen chamber and
preparation was carried out under a nitrogen atmosphere.

[0435] First, the above-mentioned substrate was heat-treated for 10
minutes at 1500° C. under a nitrogen atmosphere. Then, a liquid
obtained by mixing, in chlorobenzene, 3.0% by mass of 1:0.8 mixture of
P3HT (produced by Plectronics, Inc.: regioregular-poly-3-hexylthiophene)
and PCBM (produced by Frontier Carbon Corporation:
6,6-phenyl-C61-butyric acid methyl ester) was prepared, and then
applied onto the resulting substrate, while filtering with a filter, so
that the thickness was 100 nm, followed by drying while leaving at an
ambient temperature. Subsequently, a heat treatment at 150° C. for
15 minutes was conducted, whereby a photoelectric conversion layer was
formed.

[0436] Next, the substrate on which the aforementioned series of function
layers were formed was moved into the chamber of a vacuum evaporation
apparatus, and, after the inside of the vacuum evaporation apparatus was
evacuated to 1×10-4 Pa or less, lithium fluoride was
accumulated to a thickness of 0.6 nm at an evaporation rate of 0.01
nm/sec, and, subsequently, metallic Al was accumulated to a thickness of
100 nm at an evaporation rate of 0.2 nm/sec through a shadow mask having
a width of 2 mm (vacuum evaporation was conducted by orthogonally
crossing the masks so that the photo receiving portion became 2×2
mm), whereby a second electrode was formed.

[0437] Obtained Organic photoelectric conversion elements 1 to 17 of each
set were transferred to a nitrogen chamber, and sealing was conducted
according to the following sealing method. Thus, Organic photoelectric
conversion elements 1 to 17 of each set, each element having 2×2 mm
photo receiving portions were prepared.

(Sealing of Organic Photoelectric Conversion Elements 1 to 17)

[0438] Under a circumstance purged by a nitrogen gas (an inert gas), two
sheets of gas barrier films which were the same as that used for the
substrate were applied with an epoxy-photocurable adhesive as a sealant
on the surface on which the gas barrier layer. The above described
organic photoelectric conversion element was sandwiched between the two
gas barrier films while the surfaces having the gas barrier layer were
arranged inside, and the gas barrier films were tightly adhered. Then,
the organic photoelectric conversion element was irradiated with UV light
from the substrate side of one side for hardening.

[0439] As described above, Organic photoelectric conversion elements 1 to
17 (including both sets of having been subjected to the bending treatment
and having not been subjected to the bending treatment).

[0440] Each of Organic photoelectric conversion elements 1 to 17 was
irradiated with light of 100 mW/cm2 from a solar simulator (AM 1.5 G
filter). By evaluating an I-V property while placing a mask having an
effective area of 4.0 mm2 on the photo receiving portion, a short
circuit current density Jsc (mA/cm2), an open circuit voltage Voc
(V) and a fill factor FF (%) were determined to evaluate the energy
conversion efficiency PCE(%) calculated according to following Formula 1
for each of the four photo receiving portions formed on the same element.
Then, an average of the above four energy conversion efficiencies was
estimated.

PCE(%)=[Jsc(mA/cm2)×Voc(V)×FF(%)]/100 mW/cm2.
Formula 1

[0441] The energy conversion efficiency as an initial cell property was
measured, and then the degree of time degradation of the property was
evaluated from the residual ratio of the energy conversion efficiency
after an enforced degradation test in which the element was stored at
60° C. under 90% RH for 1000 hours.

[0442] The ratio of [0443] energy conversion efficiency after enforced
degradation test/initial energy conversion efficiency was evaluated. With
respect to the photoelectric conversion efficiency, evaluation was
conducted on the barrier films which were subjected to the above bending
treatment. 5: 80% or more 4: 70% or more, but less than 80% 3: 40% or
more, but less than 70% 2: 20% or more, but less than 40% 1: less than
20%

[0445] It is clear from Table 3 that, when compared with the comparative
Organic photoelectric conversion elements 14 to 16, each of Organic
photoelectric conversion elements 1 to 13 and 17 of the present invention
shows a remarkably superior photoelectric conversion efficiency of the
organic photoelectric conversion element.